WO2015197891A1 - Heterogenisable palladium nhc complexes - Google Patents
Heterogenisable palladium nhc complexes Download PDFInfo
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- WO2015197891A1 WO2015197891A1 PCT/ES2015/070235 ES2015070235W WO2015197891A1 WO 2015197891 A1 WO2015197891 A1 WO 2015197891A1 ES 2015070235 W ES2015070235 W ES 2015070235W WO 2015197891 A1 WO2015197891 A1 WO 2015197891A1
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- -1 palladium N-heterocyclic carbene complexes Chemical class 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 37
- 125000002883 imidazolyl group Chemical group 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 150000003839 salts Chemical group 0.000 claims description 19
- 230000009466 transformation Effects 0.000 claims description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical group CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 125000005544 phthalimido group Chemical class 0.000 claims description 12
- 150000003141 primary amines Chemical group 0.000 claims description 12
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000013522 chelant Substances 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 7
- 150000007942 carboxylates Chemical class 0.000 claims description 7
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 150000004703 alkoxides Chemical class 0.000 claims description 5
- 238000005755 formation reaction Methods 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 claims description 5
- 150000007944 thiolates Chemical class 0.000 claims description 5
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000012512 characterization method Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 150000003378 silver Chemical class 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000006263 metalation reaction Methods 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000010511 deprotection reaction Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims 12
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 5
- 238000002955 isolation Methods 0.000 claims 3
- 150000003973 alkyl amines Chemical class 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- 150000001450 anions Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000006249 magnetic particle Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 231
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 84
- 238000005481 NMR spectroscopy Methods 0.000 description 39
- 239000007787 solid Substances 0.000 description 32
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical class C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 28
- 238000002360 preparation method Methods 0.000 description 28
- 150000004693 imidazolium salts Chemical class 0.000 description 23
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical class C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 8
- 229910001923 silver oxide Inorganic materials 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000003708 ampul Substances 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910018540 Si C Inorganic materials 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229910010271 silicon carbide Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- CHZXTOCAICMPQR-UHFFFAOYSA-N 2-(2-bromoethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCBr)C(=O)C2=C1 CHZXTOCAICMPQR-UHFFFAOYSA-N 0.000 description 4
- 0 CC(C)(CN(C1*(*)C([*@@]2C=CC)N=C(C)N)C=CN1C(C)(C)CC2(C)N)N Chemical compound CC(C)(CN(C1*(*)C([*@@]2C=CC)N=C(C)N)C=CN1C(C)(C)CC2(C)N)N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000013256 coordination polymer Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 4
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 3
- 238000007126 N-alkylation reaction Methods 0.000 description 3
- 229910003691 SiBr Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000295 complement effect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000914 diffusion-ordered spectroscopy Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 125000005543 phthalimide group Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- XEFLCLZQKDDENB-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)imidazole Chemical compound CC1=CC(C)=CC(C)=C1N1C=NC=C1 XEFLCLZQKDDENB-UHFFFAOYSA-N 0.000 description 2
- OWSXDWUAPKBLOI-UHFFFAOYSA-N 1-[2,6-di(propan-2-yl)phenyl]imidazole Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N1C=NC=C1 OWSXDWUAPKBLOI-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VOLGAXAGEUPBDM-UHFFFAOYSA-N $l^{1}-oxidanylethane Chemical compound CC[O] VOLGAXAGEUPBDM-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- KGLPWQKSKUVKMJ-UHFFFAOYSA-N 2,3-dihydrophthalazine-1,4-dione Chemical compound C1=CC=C2C(=O)NNC(=O)C2=C1 KGLPWQKSKUVKMJ-UHFFFAOYSA-N 0.000 description 1
- GNENVASJJIUNER-UHFFFAOYSA-N 2,4,6-tricyclohexyloxy-1,3,5,2,4,6-trioxatriborinane Chemical compound C1CCCCC1OB1OB(OC2CCCCC2)OB(OC2CCCCC2)O1 GNENVASJJIUNER-UHFFFAOYSA-N 0.000 description 1
- DKWVMFVZPTZPJE-UHFFFAOYSA-N 2-(1h-imidazol-2-ylmethyl)-1h-imidazole Chemical compound N=1C=CNC=1CC1=NC=CN1 DKWVMFVZPTZPJE-UHFFFAOYSA-N 0.000 description 1
- JMFBXUMHVSZUKY-UHFFFAOYSA-N 3-bromopropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCBr JMFBXUMHVSZUKY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 208000022120 Jeavons syndrome Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000001500 aryl chlorides Chemical class 0.000 description 1
- 125000003943 azolyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- LWHYKTAISUZRAD-UHFFFAOYSA-L palladium(2+);carbonate Chemical compound [Pd+2].[O-]C([O-])=O LWHYKTAISUZRAD-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D233/24—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/10—Silver compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the invention frames the chemical and pharmaceutical sector, more specifically on catalysts for organic synthesis processes based on metal complexes, and more specifically on N-heterocyclic palladium carbine complexes functionalized for immobilization on magnetically separable supports. STATE OF THE TECHNIQUE
- catalysts based on metal complexes are characterized by their high activity and selectivity in a multitude of chemical processes that are carried out under mild phase conditions homogeneous
- the industrial use of homogeneous catalysis applied to the production of drugs, agrochemicals and other products of fine chemistry is quite limited.
- the main reasons for the above are, on the one hand, the cost of the complexes and, on the other, the greatest difficulty in separating them from the products compared to heterogeneous catalysts.
- catalysts in particular palladium and phosphorus-free ligands, that combine a distinctive behavior with high TON values (of the English turnover number), with which to implement "clean productions” in which They can easily and efficiently separate allowing reuse, or continuous use, and in which you can do without the expensive operations of metal purification of the products.
- NCMs N-heterocyclic carbine type
- the present invention proposes the preparation of new NHC palladium complexes (CPs) functionalized with groups suitable for subsequent heterogeneization on magnetic particles (PMs) of iron oxide.
- This method provides well-defined unique metallic species, in which NHC ligands strongly fix the metal centers and protect them during catalysis, while being covalently supported through inert "Y" groups to particles coated with a material as well. inert, while the superparamagnetism of the nucleus of the particle to which they are associated allows its separation from the medium by applying a magnetic field.
- NHC ligand precursors substituted by complementary (G c ) terminal groups and the like or necessary to synthesize CPs of the l-lll types an imidazolium salt substituted with a protected amine in the form of a phthalimide group has been described (Harjani, JR , et al. 2008), three others substituted with a primary amine as a group complementary "G c " (Busetto, L. et al. 2008; Bailar ⁇ n, B., et al. 2012; Ohara, H., et al. 2012), five others in which this group is triethoxysilyl (Chi, YS, et al. 2004; Trilla, M., et al.
- CPs bis (NHC) have been described with the structure referred to as type II in which the "G c " is trialkoxysilyl, using similar procedures (Kunze, K., et al. PCT / US2011 / 046155; Tyrrell, E., et al. 2011; Berardi, S., et al. 2010), or different (Yang, H., et al. 2009; Polshettiwar, V., et al. 2008; Corma, A., et al. 2007; Lee , S.-M., et al. 2007, 79; Karimi, B., et al. 2006), to employees in the context of the present invention.
- the present invention comprises a method of preparing new CPs that, once formed, can be heterogeneized on PMs, providing PMCs with unique palladium species, well defined and strongly fixed to the support, which are of interest as recoverable catalysts (Mart ⁇ nez-Olid , FJ, et al. P201400505).
- the invention is related to new CPs that have typologies I, II and III.
- the invention is related to the methods of synthesis of said CPs of types I, II and III and their precursors.
- the invention comprises the synthesis of CPs with NHC ligands substituted by complementary (G c ) terminal groups of an alkyl chain, which are useful for the formation of PMCs by post-synthetic immobilization of complexes to PMs that have a coating with surface groups (G s ) suitable to form "Y" covalent bonds.
- G s surface groups
- the CP to be supported comprises mono (NHC), bis (NHC) and bis (NHC) -chelate complexes, in which "L” is a neutral monodentate ligand U with donor nitrogen (type I), preferably a pyridine, and "R” is an alkyl or aryl or alkylaryl substituent, or "L” is another NHC anchor ligand with the same “R” (type II), or “L” is another NHC anchor ligand in which "R” is a chain alkyl bridge between the two NHC ligands (type III), respectively.
- mono (NHC), bis (NHC) and bis (NHC) -chelate complexes in which "L” is a neutral monodentate ligand U with donor nitrogen (type I), preferably a pyridine, and "R” is an alkyl or aryl or alkylaryl substituent, or “L” is another NHC anchor ligand with the same “R” (type II), or “L” is another NHC anchor
- X is a monoanionic substituent, preferably a halide
- G c is a functional group capable of undergoing condensation reactions, preferably a trialkoxysilyl or primary amine, which is located at end of an alkyl chain of n carbons, preferably between 1 and 4.
- the heterocyclic rings are linked through an alkyl chain of n 'links, preferably between 1 and 3.
- R may be an alkyl, aryl or alkylaryl group, containing between 1 and 20 carbon atoms, and may be substituted by groups without active protons (halogen, sulphonate, carboxylate, ether, thioether, ketone, sulfoxide, ester, amide, nitrile ); where alternatively R may be another chain with the phthalimido group; where X " can be an anionic species, preferably a halide; and where the spacer between the protective group and the heterocycle is defined by a chain length of n links that can be comprised between 1 and 4 carbons.
- N-substituted imitols preferably , but not exclusively, unsubstituted in the heterocyclic carbon in position 2, by N-alkylation reactions with (haloalkyl) trialkoxysilanes, to form and isolate imidazolium 2 (Si) salts with a trialkoxysilyl group,
- X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate.
- X " and n have been defined above in transformation a) and n 'in transformation g); and where additionally the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate i) transform chelate complexes 5, by conventional methods of Gabriel's synthesis (acidic or basic hydrolysis), or preferably by Ing-Manske's method using hydrazine, to form and isolate bis (NHC) chelate complexes of type lll (A) with primary terminal chain amine groups, in which the carbine ligands are coordinated, preferably but not exclusively, by their carbon 2,
- X and n have been previously defined in transformation a) and n 'in transformation g); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate.
- Figure 1 Schematic representation of the heterogeneization of the CPs object of the present invention.
- the present invention is further illustrated by the following illustrative, but not limiting, examples in which experimental procedures, spectroscopic and analytical data of palladium complexes and their precursors are indicated.
- Example 2 Preparation of the imidazolium salt 1.2.
- Compound 1.2 was prepared similarly to that described for salt 1.1 of Example 1, starting from N-mesitylimidazole (0.50 g, 2.7 mmol) and N- (2-bromoethyl) phthalimide (0.34 g, 1.4 mmol), in THF (40 mL), at 90 ° C and for 16 h.
- Compound 1.2 was obtained as a white oiled solid (0.56 g, 95%).
- Example 4 Preparation of the imidazolium salt 2 (Si) 1.
- a 50 mL ampoule with (3-bromopropyl) triethoxysilane (0.29 g, 1.0 mmol)
- 2 mL of dry CH 3 CN was added.
- the N-methylimidazole (0.08 g, 1.0 mmol) was then added.
- the resulting yellow solution was left under stirring at 100 ° C for 16 h, then the solvent was evaporated.
- the resulting yellow oil was washed with hexane (2 x 15 mL), obtaining compound 2 (Si) 1 as a yellow oil (0.33 g, 89%).
- Compound 2 (Si) 2 was prepared similarly to that described for salt 2 (Si) 1 of Example 4, starting from N-mesitylimidazole (0.22 g, 1.2 mmol) and the brominated derivative (0, 34 g, 1.2 mmol), in CH 3 CN (2.5 mL), at 100 ° C and for 24 h. All solid reagents were previously kept under vacuum for 10 min. Compound 2 (Si) 2 was obtained as an oiled white solid (0.55 g, 98%). Anal. Cale, for C 2 i H 35 O 3 N 2 SiBr 0, 1 H 2 O (489,530): C, 53.29; H, 7.50; N, 5.92%.
- Compound 2 (Si) 3 was prepared similarly to that described for salt 2 (Si) 1 of Example 4, starting from N- (2,6-diisopropylphenyl) imidazole (0.28 g, 1.2 mmol) and the brominated derivative (0.34 g, 1.2 mmol), in CH 3 CN (2.5 mL), at 100 ° C and for 24 h. All solid reagents were held in vacuo for 10 min before use. Compound 2 (Si) 3 was obtained as a white solid of oily appearance (0.61 g, 99%). Anal.
- Example 7 Preparation of the imidazolium salt 2 (A) 1. Hydrazine (2.10 ml_, 43.1 mmol) was added to a 50 ml vial with the imidazolium salt 1.1 described in Example 1 (1.40 g, 4.3 mmol) in 25 ml_ of 2-propanol and It was heated at 40 ° C overnight. The initial white suspension was returned to a clear solution with the progress of the reaction to finally precipitate a white solid that corresponds to the by-product of the deprotection, phthalylhydrazine. The mixture was cooled, filtered and evaporated to obtain the desired product 2 (A) 1 as a yellow oil (0.80 g, 95%). Anal.
- Compound 2 (A) 2 was prepared similarly to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1.2 described in Example 2 (1.29 g, 2.9 mmol) and hydrazine (1.43 mL, 29.0 mmol), in isopropanol, at 40 ° C and overnight. After filtering, evaporating and washing with hexane, the imidazolium 2 (A) 2 salt was obtained as a yellow oil (0.87 g, 95%). Anal. Cale, for C 14 H 20 N 3 Br 0.7H 2 O (322.84): C, 52.08; H, 6.68; N, 13.02%; Found: C, 51, 82; H, 6.34; N, 13.24%.
- Example 9 Preparation of the imidazolium salt 2 (A) 3.
- Compound 2 (A) 3 was prepared similarly to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1.3 described in Example 3 (0.46 ml_, 9.50 mmol) and hydrazine (0.46 ml_, 9.50 mmol), in isopropanol, at 40 ° C and overnight. After filtering, evaporating and washing with hexane, the imidazolium 2 (A) 2 salt was obtained as a yellow oil (0.31 g, 92%). Anal.
- Compound 1 (Si) 2 was prepared as described for complex 1 (Si) 1 of Example 10, starting from the imidazolium salt 2 (Si) 2 described in Example 5 (0.57 g, 1, 2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.26 g, 8.4 mmol), in 12 ml_ of 4-picoline, at 100 ° C and for 16 h. Compound 1 (Si) 2 was obtained as an orange powdery solid (0.99 g, 98%). Anal.
- Compound 1 (Si) 3 was prepared in a manner similar to that described for complex 1 (Si) 1 of Example 10, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (0.62 g, 1 , 2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.28 g, 8.4 mmol), in 12 mL of 4-picoline, at 100 ° C and for 16 h. Compound 1 (Si) 3 was obtained as an orange powdery solid (0.99 g, 98%). Anal.
- Example 13 Preparation of the silver complex 3 (Si) 1.
- the imidazolium 2 (Si) 1 salt described in Example 4 (1.28 g, 3.5 mmol) and the silver oxide (0.40 g, 1.7 mmol) were weighed in a 50 mL ampoule. and it was empty for 10 min.
- the solid was suspended in 10 mL of dichloromethane under argon and the mixture was allowed to stir at room temperature for 16 h in the absence of light.
- NMR 13 C ⁇ 1 H ⁇ (CDCI 3, 75 MHz): Isomer anti: 5 8.7 (SiCH 2), 18.2 (CH 3 CH 2 0), 25.6 (SiCH 2 CH 2) 38, 9 (Imz-Me), 54, 1 (CH 2 lmz), 58.3 (CH 3 CH 2 0), 121, 2 and 122.1 (Imz-C 4 and C 5 ), 181, 7 (Imz- C 2 ).
- Compound 3 (Si) 2 was prepared as described for complex 3 (Si) 1 of Example 13, starting from the imidazolium 2 (Si) 2 salt described in Example 5 (2.69 g, 5.7 mmol) and silver oxide (0.66 g, 2.8 mmol).
- Complex 3 (Si) 2 was obtained as a yellow oily solid (3.07 g, 98%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2 ] [AgBr 2 ] that results in rotámeros syn and anti (70:30) in balance. Anal.
- Compound 3 (Si) 3 was prepared as described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (2.50 g, 5.2 mmol) and silver oxide (0.60 g, 2.6 mmol).
- Complex 3 (Si) 3 was obtained as a yellow oily solid (3.14 g, 98%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2 ] [AgBr 2 ] which results in rotámeros syn and anti (70:30) in balance. Anal.
- NMR 13 C ⁇ 1 H ⁇ (CDCI 3, 75 MHz): Isomer anti: 5 7.5 (SiCH 2), 18.3 (CH 3 CH 2 0), 24.3 (CH (CH 3) 2), 25.4 (SiCH 2 CH 2 ), 28, 1 (CH (CH 3 ) 2 ), 54, 1 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 121, 5 and 123.7 ( Imz-C 4 and C 5 ), 124.2 (p-Ph), 129.7 (m-Ph), 145.6 (o-Ph), 145.9 (/ pso-Ph).
- Compound 3 (A) 1 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 1 described in Example 7 (0.80 g, 3 , 7 mmol) and silver oxide (0.43 g, 1.9 mmol).
- Complex 3 (A) 1 was obtained as a yellow oily solid (1.03 g, 88%).
- Compound 3 (A) 2 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 2 described in Example 8 (3.20 g, 10 , 0 mmol) and silver oxide (1.18 g, 5.1 mmol).
- Complex 3 (A) 2 was obtained as a yellow oily solid (3.60 g, 86%).
- Compound 3 (A) 3 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 3 described in Example 9 (3.60 g, 10 , 3 mmol) and silver oxide (1.18 g, 5.1 mmol).
- Complex 3 (A) 3 was obtained as a yellow oily solid (4.30 g, 90%).
- Example 19 Preparation of the palladium complex ll (Si) 1.
- the solids were subjected to vacuum for 5 min, the solid was dissolved under argon in 10 mL of dichloromethane and the resulting orange solution was allowed to stir at room temperature for 1 h.
- Example 20 Preparation of palladium complex ll (Si) 2.
- Compound ll (Si) 2 was prepared in the same manner as compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (Si) 2 described in Example 14 (0.45 g, 0.81 mmol) and of PdBr 2 (COD) (0.15 g, 0.41 mmol).
- Complex ll (Si) 2 was obtained as a yellow powdery solid (0.83 g, 97%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (56:44) in equilibrium.
- Example 21 Preparation of palladium complex ll (Si) 3.
- Compound ll (Si) 3 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (Si) 3 described in Example 15 (0.44 g, 0.70 mmol ) and PdBr 2 (COD) (0.13 g, 0.35 mmol).
- Complex ll (Si) 3 was obtained as a yellow powdery solid (0.75 g, 95%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (60:40) in equilibrium.
- Example 22 Preparation of the palladium complex ll (A) 1.
- Compound ll (A) 1 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 1 described in Example 16 (1, 00 g, 3.2 mmol ) and PdBr 2 (COD) (0.60 g, 1.6 mmol).
- Complex ll (A) 1 was obtained as an oily yellow solid (0.70 g, 85%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 1] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (30:70) rotamers in equilibrium. Anal.
- Compound ll (A) 2 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 2 described in Example 17 (0.50 g, 1.2 mmol ) and PdBr 2 (COD) (0.22 g, 0.60 mmol).
- Complex ll (A) 2 was obtained as an oily yellow solid (0.38 g, 88%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 2] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (20:80) rotamers in equilibrium.
- Example 24 Preparation of the palladium complex ll (A) 3.
- Compound ll (A) 3 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 3 described in Example 18 (0.50 g, 0.85 mmol ) and PdBr 2 (COD) (0.16 g, 0.42 mmol).
- Complex ll (A) 3 was obtained as an oily yellow solid (0.58 g, 84%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 3] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (25:75) rotamers in equilibrium. Anal.
- Example 25 Preparation of the imidazolium salt 4.4.
- Example 26 Preparation of palladium chelate complex 5.4.
- the bisimidazolium salt 4.4 described in Example 25 (0.50 g, 0.76 mmol) was weighed in a 15 mL ampoule with screw cap and dissolved in 1 mL of DMSO, an equivalent of acetate was added to that solution palladium (0.17 g, 0.76 mmol).
- the resulting suspension was heated at 50 ° C with stirring for 2 h. After these 2 h, the temperature was gradually increased to 1 10 ° C over 3 h.
- the resulting reddish solution was passed through a celite column about 2.0 cm high and 1.5 cm in diameter.
- Example 26 The palladium 5.4 complex described in Example 26 (1.00 g, 1.3 mmol) was weighed in a 25 mL ampoule and dissolved in 2 mL of dry CH 3 CN. On the suspension formed, 40 equivalents of hydrazine (2.50 mL, 52.0 mmol) were added, giving a clear solution. After one hour of reaction at room temperature, the phthalyhydhydrazine formed was filtered, the solvent was evaporated and washed with hot THF using a soxhlet kit, the product lll (A) 4 being obtained as a beige solid (0.50 g, 82% ). Anal. Cal.
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Abstract
The invention relates to a method for producing novel palladium N-heterocyclic carbene complexes of different topologies (I, II and III), which, once formed, can be heterogenised on magnetic particles, providing magnetic particles comprising the supported complexes with unique species of palladium, which are clearly defined and firmly fixed to the support, and of interest as recoverable catalysts.
Description
COMPLEJOS NHC DE PALADIO HETEROGENEIZABLES NHC COMPLEXES OF HETEROGENEIZABLE PALADIO
SECTOR DE LA TÉCNICA La invención se enmarca el sector químico y farmacéutico, más concretamente sobre catalizadores para procesos de síntesis orgánica basados en complejos metálicos, y más específicamente en complejos carbeno N-heterocíclico de paladio funcionalizados para su inmovilización sobre soportes magnéticamente separables. ESTADO DE LA TÉCNICA TECHNICAL SECTOR The invention frames the chemical and pharmaceutical sector, more specifically on catalysts for organic synthesis processes based on metal complexes, and more specifically on N-heterocyclic palladium carbine complexes functionalized for immobilization on magnetically separable supports. STATE OF THE TECHNIQUE
Como consecuencia del fácil acceso de los sustratos a sus centros activos y al entorno modificable y controlable de éstos, los catalizadores basados en complejos metálicos se caracterizan por su elevada actividad y selectividad en multitud de procesos químicos que se llevan a cabo en condiciones suaves en fase homogénea. Sin embargo, en la actualidad el uso industrial de la catálisis homogénea aplicado a la producción de fármacos, agroquímicos y otros productos de la química fina, es bastante limitado. Las razones principales de lo anterior son, por un lado, el coste de los complejos y, por otro, la mayor dificultad para separarlos de los productos comparada con catalizadores heterogéneos. Estos obstáculos son especialmente relevantes con complejos de metales del grupo del platino (Pt, Pd, Ir, Rh, Os, Ru), sobre los que, además, existen directrices y regulaciones ambientales y sanitarias que restringen drásticamente los niveles permisibles de contaminación por metales en muchas producciones (e.g., European Medicines Agency 2008). As a result of the easy access of the substrates to their active centers and to the modifiable and controllable environment of these, catalysts based on metal complexes are characterized by their high activity and selectivity in a multitude of chemical processes that are carried out under mild phase conditions homogeneous However, currently the industrial use of homogeneous catalysis applied to the production of drugs, agrochemicals and other products of fine chemistry, is quite limited. The main reasons for the above are, on the one hand, the cost of the complexes and, on the other, the greatest difficulty in separating them from the products compared to heterogeneous catalysts. These obstacles are especially relevant with platinum group metal complexes (Pt, Pd, Ir, Rh, Os, Ru), on which, in addition, there are environmental and sanitary guidelines and regulations that drastically restrict the permissible levels of metal contamination in many productions (eg, European Medicines Agency 2008).
Existe, por tanto, un enorme mercado potencial para catalizadores metálicos que aúnen las ventajas de los catalizadores de fase homogénea (i.e., alta actividad y selectividad en condiciones suaves) con las de los de fase heterogénea (i.e., elevada productividad y fácil recuperación y reciclado). Una clasificación general de las estrategias que hasta ahora se han explorado para ello comprende: i) catálisis multifásica o confinamiento del catalizador homogéneo en una fase distinta a la de sustrato y productos, incluyendo fases acuosas, líquidos iónicos, fluidos supercríticos o disolventes fluorados; ii) utilización de membranas de nanofiltración con catalizadores de peso molecular agrandado mediante su inmovilización a soportes solubles como dendrímeros, polímeros o polisisesquioxanos; y iii) heterogeneización o inmovilización de complejo metálico soluble a soportes insolubles, tanto orgánicos como inorgánicos. En general, estos intentos no han resultado
en procesos comercialmente viables por diversos motivos, encontrando que los más frecuentes son el lixiviado del centro activo y/o su degradación, que resultan en la contaminación metálica de los productos y/o en pérdidas fatales de productividad, actividad y selectividad. There is, therefore, a huge potential market for metal catalysts that combine the advantages of homogeneous phase catalysts (ie, high activity and selectivity under mild conditions) with those of heterogeneous phase (ie, high productivity and easy recovery and recycling). ). A general classification of the strategies that have been explored so far includes: i) multiphasic catalysis or confinement of the homogeneous catalyst in a different phase from the substrate and products, including aqueous phases, ionic liquids, supercritical fluids or fluorinated solvents; ii) use of nanofiltration membranes with enlarged molecular weight catalysts by immobilization to soluble supports such as dendrimers, polymers or polysisesquioxanes; and iii) heterogeneization or immobilization of soluble metal complex to insoluble supports, both organic and inorganic. In general, these attempts have not resulted in commercially viable processes for various reasons, finding that the most frequent are the leaching of the active center and / or its degradation, resulting in metallic contamination of the products and / or in fatal losses of productivity, activity and selectivity.
El caso particular de paladio, conocido por su utilidad para catalizar un rango amplio de transformaciones en síntesis orgánica, convencionalmente asociado a ligandos organofosforados, no es una excepción: son muy pocos los procesos industriales implantados en los que intervienen sus complejos solubles (de Vries, J. G. 2012) y en ellos generalmente ha sido necesario desarrollar procedimientos específicos y costosos para eliminar los restos tóxicos metálicos y fosforados. Según de Vries, en el lustro anterior a 2012 sólo el 6-7% de las etapas sintéticas de la industria farmacéutica implicaron la catálisis homogénea, destacando que el 50% de ellas correspondían a los fármacos introducidos más recientemente. The particular case of palladium, known for its usefulness in catalyzing a wide range of transformations in organic synthesis, conventionally associated with organophosphorus ligands, is no exception: there are very few industrial processes implanted in which their soluble complexes (de Vries, JG 2012) and in them it has generally been necessary to develop specific and expensive procedures to eliminate metallic and phosphorus toxic residues. According to de Vries, in the five years before 2012, only 6-7% of the synthetic stages of the pharmaceutical industry involved homogeneous catalysis, highlighting that 50% of them corresponded to the most recently introduced drugs.
Sería por lo tanto deseable disponer de catalizadores, en particular de paladio y libres de ligandos fosforados, que combinen un comportamiento distintivo con altos valores de TON (del inglés turnover number), con los que llegar a implementar "producciones limpias" en las que se puedan separar fácil y eficientemente posibilitando su reutilización, o su uso en continuo, y en las que se pueda prescindir de las costosas operaciones de purificación metálica de los productos. It would therefore be desirable to have catalysts, in particular palladium and phosphorus-free ligands, that combine a distinctive behavior with high TON values (of the English turnover number), with which to implement "clean productions" in which They can easily and efficiently separate allowing reuse, or continuous use, and in which you can do without the expensive operations of metal purification of the products.
Unos ligandos que recientemente han aparecido como una alternativa muy atractiva a los organofosforados son los de tipo carbeno N-heterocíclico (NHC). Los NHCs proporcionan enlaces fuertes, que resultan en complejos metálicos muy robustos y excelentes para catalizar un rango muy amplio de procesos en fase homogénea, en los que las características estéreo-electrónicas del ligando juegan un papel estabilizador importante (Diez-González, S., et al. 2009). Para inmovilizar catalizadores metálicos, entre otros soportes disponibles en la actualidad, se han utilizado nanopartículas magnéticas (NPMs) con diversos tipos de ligandos anclados covalentemente a la superficie, (Baig, R. B. N., et al. 2013; Shylesh, S., et al. 2010). Existen también descripciones en las que se han empleado complejos NHC de paladio heterogeneizados a través de grupos alquilsilóxido sobre NPMs desnudas (Stevens, P. D., et al. Chem. Commun. 2005; Zheng, Y., et al. 2006), mediante grupos bencilo sobre NPMs recubiertas de poliestireno (Stevens, P. D., et al. Org. Lett. 2005), y
grupos arilsiloxano sobre microesferas magnéticas (Yang, H., et al. 2012) o NPMs recubiertas de sílice (Yang, H., et al. 2011). Se ha demostrado que todos ellos son activos en diversas reacciones de acoplamiento cruzado (i.e., Suzuki-Miyaura, Heck- Mizoroki y Sonogashira), son recuperables magnéticamente y la mayoría han sido reutilizados. De los anteriores sólo en un caso (Yang, H., et al. 2011) se ha determinado el contenido de paladio en los productos, pero únicamente tras el primer uso del catalizador. En todos ellos el procedimiento de soportado del complejo metálico sigue la secuencia: 1) funcionalización del soporte con sales de imidazolio, que son precursoras de ligandos NHC; 2) metalación del soporte funcionalizado anterior con acetilacetonato o acetato de paladio ([Pd(acac)2] ó [Pd(OAc)2]). La desventaja de esta metodología, que por otro lado es la habitual con cualquier tipo de soporte y ligando, es la imposibilidad de poder controlar tanto la formación de complejos con un único entorno de coordinación, como la presencia de restos metálicos adsorbidos y no anclados covalentemente. En este sentido, recientemente se ha comprobado que, usando gel de sílice como soporte, los resultados catalíticos son mucho mejores cuando se inmoviliza el complejo NHC de paladio preformado que cuando éste se sintetiza sobre la superficie del gel de sílice (Tyrrell, E, et al. 2011). Some ligands that have recently appeared as a very attractive alternative to organophosphates are those of the N-heterocyclic carbine type (NHC). The NHCs provide strong bonds, which result in very robust and excellent metal complexes to catalyze a very wide range of homogeneous phase processes, in which the stereo-electronic characteristics of the ligand play an important stabilizing role (Diez-González, S., et al. 2009). To immobilize metal catalysts, among other supports currently available, magnetic nanoparticles (NPMs) with various types of ligands covalently anchored to the surface have been used, (Baig, RBN, et al. 2013; Shylesh, S., et al. 2010). There are also descriptions in which heterogeneized palladium NHC complexes have been used through alkylsiloxide groups on bare NPMs (Stevens, PD, et al. Chem. Commun. 2005; Zheng, Y., et al. 2006), by benzyl groups on polystyrene coated NPMs (Stevens, PD, et al. Org. Lett. 2005), and arylsiloxane groups on magnetic microspheres (Yang, H., et al. 2012) or silica coated NPMs (Yang, H., et al. 2011). All of them have been shown to be active in various cross-coupling reactions (ie, Suzuki-Miyaura, Heck-Mizoroki and Sonogashira), are magnetically recoverable and most have been reused. Of the above, only in one case (Yang, H., et al. 2011) has the content of palladium in the products been determined, but only after the first use of the catalyst. In all of them, the metal complex support procedure follows the sequence: 1) support functionalization with imidazolium salts, which are precursors of NHC ligands; 2) Metalation of the previous functionalized support with acetylacetonate or palladium acetate ([Pd (acac) 2 ] or [Pd (OAc) 2 ]). The disadvantage of this methodology, which on the other hand is the usual one with any type of support and ligand, is the impossibility of being able to control both the formation of complexes with a single coordination environment, such as the presence of adsorbed and non-covalently anchored metal remains . In this regard, it has recently been found that, using silica gel as a support, the catalytic results are much better when the NHC complex of preformed palladium is immobilized than when it is synthesized on the surface of the silica gel (Tyrrell, E, et al. 2011).
La presente invención propone la preparación de nuevos complejos NHC de paladio (CPs) funcionalizados con grupos adecuados para su heterogeneizacion a posteriori sobre partículas magnéticas (PMs) de óxido de hierro. Este método proporciona especies metálicas únicas bien definidas, en las que los ligandos NHC fijan fuertemente los centros metálicos y los protegen durante la catálisis, a la vez que se encuentran soportadas covalentemente a través de grupos inertes "Y" a partículas recubiertas de un material también inerte, mientras que el superparamagnetismo del núcleo de la partícula a la que están asociadas permite su separación del medio aplicando un campo magnético. Estas partículas magnéticas con los catalizadores soportados (PMCs) dan lugar a dispersiones estables en agua, catalizan reacciones de acoplamiento carbono-carbono en medio acuoso en condiciones suaves, incluso con cloruros de arilo, se recuperan sin degradación por simple separación magnética, se pueden reutilizar llegando a valores de TON muy elevados y no sufren lixiviado metálico (Martínez-Olid, F. J., et al. P201400505). The present invention proposes the preparation of new NHC palladium complexes (CPs) functionalized with groups suitable for subsequent heterogeneization on magnetic particles (PMs) of iron oxide. This method provides well-defined unique metallic species, in which NHC ligands strongly fix the metal centers and protect them during catalysis, while being covalently supported through inert "Y" groups to particles coated with a material as well. inert, while the superparamagnetism of the nucleus of the particle to which they are associated allows its separation from the medium by applying a magnetic field. These magnetic particles with the supported catalysts (PMCs) give rise to stable dispersions in water, catalyze carbon-carbon coupling reactions in aqueous medium under mild conditions, even with aryl chlorides, recover without degradation by simple magnetic separation, can be reused reaching very high TON values and not suffering from metallic leaching (Martínez-Olid, FJ, et al. P201400505).
Referente a precursores de ligandos NHC sustituidos por grupos complementarios (Gc) terminales y semejantes o necesarios para sintetizar CPs de los tipos l-lll, se ha descrito una sal de imidazolio sustituida con una amina protegida en forma de grupo ftalimido (Harjani, J. R., et al. 2008), otras tres sustituidas con una amina primaria como grupo
complementario "Gc" (Busetto, L. et al. 2008; Bailarín, B., et al. 2012; Ohara, H., et al. 2012), otras cinco en las que ese grupo es trietoxisililo (Chi, Y. S., et al. 2004; Trilla, M., et al. 2009; Borja, G., et al. 2012, Berardi, S., et al. 2010) y otras cinco en la que es trimetoxisililo (Kunze, K., et al. PCT/US2011/046155, Tyrrell, E., et al. 2011). Como precursores necesarios para la síntesis de complejos de tipo III, se han descrito la síntesis de bis(azolil)alcanos (Diez-Barra, E., et al. Heterocycles 1992, 34, 1365-1373). Concerning NHC ligand precursors substituted by complementary (G c ) terminal groups and the like or necessary to synthesize CPs of the l-lll types, an imidazolium salt substituted with a protected amine in the form of a phthalimide group has been described (Harjani, JR , et al. 2008), three others substituted with a primary amine as a group complementary "G c " (Busetto, L. et al. 2008; Bailarín, B., et al. 2012; Ohara, H., et al. 2012), five others in which this group is triethoxysilyl (Chi, YS, et al. 2004; Trilla, M., et al. 2009; Borja, G., et al. 2012, Berardi, S., et al. 2010) and five others in which it is trimethoxysilyl (Kunze, K., et al. PCT / US2011 / 046155, Tyrrell, E., et al. 2011). As precursors necessary for the synthesis of type III complexes, the synthesis of bis (azolyl) alkanes (Diez-Barra, E., et al. Heterocycles 1992, 34, 1365-1373) have been described.
Se conoce un único ejemplo de CP mono(NHC) relacionado con la formulación del tipo I, concretamente con el ligando NHC sustituido por una cadena con un "Gc" = trietoxisililo (Borja, G., et al. 2012), aunque se han descrito otros complejos relacionados pero sin ese tipo de sustitución (Organ, M. G., et al. CA2556850A1). A single example of mono CP (NHC) related to the formulation of type I is known, specifically with the NHC ligand substituted by a chain with a "G c " = triethoxysilyl (Borja, G., et al. 2012), although Other related complexes have been described but without such substitution (Organ, MG, et al. CA2556850A1).
Se han descrito CPs bis(NHC) con la estructura referida como de tipo II en los que el "Gc" es trialcoxisililo, utilizando procedimientos semejantes (Kunze, K., et al. PCT/US2011/046155; Tyrrell, E., et al. 2011 ; Berardi, S., et al. 2010), o distintos (Yang, H., et al. 2009; Polshettiwar, V., et al. 2008; Corma, A., et al. 2007; Lee, S.-M., et al. 2007, 79; Karimi, B., et al. 2006), a los empleados en el contexto de la presente invención. En los señalados como procedimientos semejantes, la síntesis se realiza a través de complejos intermedios de plata, que se preparan siguiendo el método estándar descrito por Lin (Wang, H. M. J., et al. 1998), pero en ningún caso se asilan, purifican y caracterizan estos agentes de transferencia de carbeno, a diferencia del procedimiento propuesto en la presente invención. No se ha descrito ningún CP de tipo III con alcoxisililos como "Gc", ni se conocen de los tipos aquí referidos como II y III en los que ese grupo es una amina primaria, a pesar de que ambas topologías de complejos de paladio, quelato o no, son abundantes en la bibliografía. CPs bis (NHC) have been described with the structure referred to as type II in which the "G c " is trialkoxysilyl, using similar procedures (Kunze, K., et al. PCT / US2011 / 046155; Tyrrell, E., et al. 2011; Berardi, S., et al. 2010), or different (Yang, H., et al. 2009; Polshettiwar, V., et al. 2008; Corma, A., et al. 2007; Lee , S.-M., et al. 2007, 79; Karimi, B., et al. 2006), to employees in the context of the present invention. In those indicated as similar procedures, the synthesis is carried out through intermediate silver complexes, which are prepared following the standard method described by Lin (Wang, HMJ, et al. 1998), but in no case are they isolated, purified and characterized these carbine transfer agents, unlike the procedure proposed in the present invention. No type III CP with alkoxysilyls has been described as "G c ", nor are there known of the types referred to herein as II and III in which this group is a primary amine, although both topologies of palladium complexes, Chelate or not, are abundant in the literature.
DESCRIPCIÓN DE LA INVENCIÓN DESCRIPTION OF THE INVENTION
La presente invención comprende un procedimiento de preparación de nuevos CPs que, una vez formados, se pueden heterogeneizar sobre PMs, proporcionando PMCs con especies de paladio únicas, bien definidas y fijadas fuertemente al soporte, que son de interés como catalizadores recuperables (Martínez-Olid, F. J., et al. P201400505). The present invention comprises a method of preparing new CPs that, once formed, can be heterogeneized on PMs, providing PMCs with unique palladium species, well defined and strongly fixed to the support, which are of interest as recoverable catalysts (Martínez-Olid , FJ, et al. P201400505).
En un primer aspecto la invención está relacionada con nuevos CPs que presentan las tipologías I, II y III.
En un segundo aspecto la invención está relacionada con los métodos de síntesis de dichos CPs de los tipos I, II y III y de sus precursores. In a first aspect the invention is related to new CPs that have typologies I, II and III. In a second aspect the invention is related to the methods of synthesis of said CPs of types I, II and III and their precursors.
PM CP PMC PM CP PMC
DESCRIPCIÓN DETALLADA DE LA INVENCIÓN DETAILED DESCRIPTION OF THE INVENTION
Específicamente, la invención comprende la síntesis de CPs con ligandos NHC sustituidos por grupos complementarios (Gc) terminales de una cadena alquílica, que son útiles para la formación de PMCs mediante la inmovilización post-sintética de los complejos a PMs que poseen un recubrimiento con grupos superficiales (Gs) adecuados para formar uniones covalentes "Y". Estas PMCs encuentran aplicaciones como catalizadores fácilmente recuperables (Martínez-Olid, F. J., et al. P201400505) Specifically, the invention comprises the synthesis of CPs with NHC ligands substituted by complementary (G c ) terminal groups of an alkyl chain, which are useful for the formation of PMCs by post-synthetic immobilization of complexes to PMs that have a coating with surface groups (G s ) suitable to form "Y" covalent bonds. These PMCs find applications as easily recoverable catalysts (Martínez-Olid, FJ, et al. P201400505)
I II III I II III
Concretamente, el CP a soportar comprende complejos mono(NHC), bis(NHC) y bis(NHC)-quelato, en los que "L" es un ligando monodentado neutro U con nitrógeno dador (tipo I), preferentemente una piridina, y "R" es un sustituyente alquilo o arilo o alquilarilo, o "L" es otro ligando anclante NHC con el mismo "R" (tipo II), o "L" es otro ligando anclante NHC en el que "R" es una cadena alquílica puente entre los dos ligandos NHC (tipo III), respectivamente. En ellos "X" es un sustituyente monoaniónico, preferentemente un haluro, y "Gc" es un grupo funcional susceptible de sufrir reacciones de condensación, preferentemente un trialcoxisililo o amina primaria, que se encuentra al
final de una cadena alquílica de n carbonos, preferentemente entre 1 y 4. Particularmente, en los CPs quelato (tipo III) los anillos heterocíclicos se encuentra unidos a través de una cadena alquílica de n' eslabones, preferentemente entre 1 y 3. Specifically, the CP to be supported comprises mono (NHC), bis (NHC) and bis (NHC) -chelate complexes, in which "L" is a neutral monodentate ligand U with donor nitrogen (type I), preferably a pyridine, and "R" is an alkyl or aryl or alkylaryl substituent, or "L" is another NHC anchor ligand with the same "R" (type II), or "L" is another NHC anchor ligand in which "R" is a chain alkyl bridge between the two NHC ligands (type III), respectively. In them "X" is a monoanionic substituent, preferably a halide, and "G c " is a functional group capable of undergoing condensation reactions, preferably a trialkoxysilyl or primary amine, which is located at end of an alkyl chain of n carbons, preferably between 1 and 4. Particularly, in the chelate CPs (type III) the heterocyclic rings are linked through an alkyl chain of n 'links, preferably between 1 and 3.
NH2NH2 (CH3)2CHOH Pd(OAc); DMSO
NH 2 NH 2 (CH 3 ) 2 CHOH Pd (OAc); DMSO
l(Si) lll(A) l (Yes) lll (A)
La síntesis de algunos de los CPs de esta invención que tienen fórmulas de los tipos I, II y III puede lograrse mediante las transformaciones indicadas en el esquema anterior. Los complejos especialmente preferidos están descritos en los ejemplos de esta invención y los métodos para preparar los complejos de los tipos l-lll y sus intermedios consiste en: a) transformar imizadoles N-sustituidos preferentemente, pero no excluyentemente, no- sustituidos en el carbono heterocíclico en posición 2, mediante reacciones de N- alquilación con N-(haloalquil)ftalimidas, para formar y aislar sales de imidazolio 1 con aminas primarias protegidas en forma de grupo ftalimido (ftal), The synthesis of some of the CPs of this invention having formulas of types I, II and III can be achieved by the transformations indicated in the previous scheme. Especially preferred complexes are described in the examples of this invention and the methods for preparing the complexes of the l-lll types and their intermediates consist of: a) transforming N-substituted imizadoles preferably, but not exclusively, non-substituted in carbon heterocyclic in position 2, by N-alkylation reactions with N- (haloalkyl) phthalimides, to form and isolate salts of imidazolium 1 with protected primary amines in the form of phthalimido (phtal) group,
1
donde R puede ser un grupo alquílico, arílico o alquilarílico, conteniendo entre 1 y 20 átomos de carbono, y puede estar sustituido por grupos sin protones activos (halógeno, sulfonato, carboxilato, éter, tioéter, cetona, sulfóxido, éster, amida, nitrilo); donde alternativamente R puede ser otra cadena con el grupo ftalimido; donde X" puede ser una especie aniónica, preferentemente un halogenuro; y donde el espaciador entre el grupo protector y el heterociclo queda definido por una longitud de cadena de n eslabones que puede estar comprendida entre 1 y 4 carbonos. transformar imizadoles N-sustituidos preferentemente, pero no excluyentemente, no- sustituidos en el carbono heterocíclico en posición 2, mediante reacciones de N- alquilación con (haloalquil)trialcoxisilanos, para formar y aislar sales de imidazolio 2(Si) con un grupo trialcoxisililo,
one where R may be an alkyl, aryl or alkylaryl group, containing between 1 and 20 carbon atoms, and may be substituted by groups without active protons (halogen, sulphonate, carboxylate, ether, thioether, ketone, sulfoxide, ester, amide, nitrile ); where alternatively R may be another chain with the phthalimido group; where X " can be an anionic species, preferably a halide; and where the spacer between the protective group and the heterocycle is defined by a chain length of n links that can be comprised between 1 and 4 carbons. transform N-substituted imitols preferably , but not exclusively, unsubstituted in the heterocyclic carbon in position 2, by N-alkylation reactions with (haloalkyl) trialkoxysilanes, to form and isolate imidazolium 2 (Si) salts with a trialkoxysilyl group,
2(Si) donde R, X" y n se han definido anteriormente en la transformación a); donde alternativamente R puede ser otra cadena con el grupo trialcoxisililo; y donde R' puede ser metilo o etilo. c) transformar las sales de imidazolio 1 , por procedimientos convencionales de la síntesis de Gabriel (hidrólisis ácida o básica), o preferentemente por el método de Ing-Manske utilizando hidracina, para formar y aislar sales de imidazolio 2(A) con un grupo amina primaria terminal de cadena,
2 (Si) where R, X " and n have been previously defined in transformation a); where alternatively R may be another chain with the trialkoxysilyl group; and where R 'may be methyl or ethyl. C) transform the imidazolium salts 1 , by conventional methods of Gabriel's synthesis (acidic or basic hydrolysis), or preferably by the Ing-Manske method using hydrazine, to form and isolate imidazolium salts 2 (A) with a primary terminal chain amine group,
2(A) donde R, X y n se han definido anteriormente en la transformación a); y donde alternativamente R puede ser otra cadena con una amina primaria terminal. d) transformar las sales de imidazolio 2(Si), por un procedimiento patentado (Organ, M. 2 (A) where R, X and n have been previously defined in transformation a); and where alternatively R may be another chain with a terminal primary amine. d) transform the imidazolium 2 salts (Si), by a patented procedure (Organ, M.
G., et al., CA2556850A1), para formar y aislar complejos mono(NHC) de tipo l(Si), en
los que el ligando carbeno se encuentra coordinado, preferente pero no excluyentemente, por su carbono 2, G., et al., CA2556850A1), to form and isolate mono (NHC) type 1 (Si) complexes, in those that the carbeno ligand is coordinated, preferably but not exclusively, by its carbon 2,
"(Si) donde R, X y n se han definido anteriormente en la transformación a) y R' en la transformación b); donde alternativamente los ligandos X pueden independientemente ser un haluro, carboxilato, hidruro, o un alquilo, alilo, arilo, alquilarilo, alcóxido, arilóxido, beta-dicetonato, tiolato sustituidos o no sustituidos; y donde U es un ligando monodentado neutro con nitrógeno dador, preferentemente una piridina que puede estar sustituida por alquilos o haluros en cualquiera de sus carbonos. transformar las sales de imidazolio 2(Si o A), mediante el procedimiento estándar descrito por Lin (Wang, H. M. J., et al. 1998) con óxido de plata, para formar y aislar complejos NHC de plata 3 (Si o A), en los que el ligando carbeno se encuentra coordinado, preferente pero no excluyentemente, por su carbono 2,
"(Si) where R, X and n have been defined above in transformation a) and R 'in transformation b); where alternatively the X ligands may independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate; and where U is a neutral monodentate ligand with donor nitrogen, preferably a pyridine that can be substituted by alkyls or halides in any of its carbons. 2 (Si or A), by the standard procedure described by Lin (Wang, HMJ, et al. 1998) with silver oxide, to form and isolate NHC complexes of silver 3 (Si or A), in which the carbine ligand is coordinated, preferential but not exclusive, by its carbon 2,
3(Si) 3(A) donde R, X y n se han definido anteriormente en la transformación a) y R' en la transformación b). transformar los complejos de plata 3(Si o A), mediante reacciones de transmetalación a precursores de paladio(n) con ligandos lábiles y de fórmula general 3 (Si) 3 (A) where R, X and n have been previously defined in transformation a) and R 'in transformation b). transform the silver complexes 3 (Si or A), by transmetalation reactions to palladium (n) precursors with labile ligands and of general formula
[PdX2L"2] (L"2 = etilendiamina, Ν,Ν,Ν'Ν'-tetrametiletilendiamina, 1 ,5-ciclooctadieno; o L" = benzonitrilo, acetonitrilo), para formar y aislar complejos bis(NHC) de tipo ll(Si o A), en los que los ligandos carbeno se encuentran coordinados, preferente pero no excluyentemente, por su carbono 2,
[PdX 2 L " 2 ] (L" 2 = ethylenediamine, Ν, Ν, Ν'Ν'-tetramethylethylenediamine, 1,5-cyclooctadiene; or L "= benzonitrile, acetonitrile), to form and isolate bis (NHC) complexes from type ll (Yes or A), in which the carbine ligands are coordinated, preferably but not exclusively, by their carbon 2,
ll(Si) 11(A) donde R, X y n se han definido anteriormente en la transformación a) y R' en la transformación b); y donde alternativamente los ligandos X pueden independientemente ser un haluro, carboxilato, hidruro, o un alquilo, alilo, arilo, alquilarilo, alcóxido, arilóxido, beta-dicetonato, tiolato sustituidos o no sustituidos. transformar bis(imidazolil)alcanos, preferente pero no excluyentemente, no- sustituidos en el carbono heterocíclico en posición 2, para formar y aislar sales de imidazolio 4 con aminas primarias protegidas en forma de grupo ftalimido (ftal) mediante reacciones de N-alquilación con N-(haloalquil)ftalimidas, ll (Si) 11 (A) where R, X and n have been previously defined in transformation a) and R 'in transformation b); and where alternatively the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate. transforming bis (imidazolyl) alkanes, preferably but not exclusively, unsubstituted in heterocyclic carbon in position 2, to form and isolate salts of imidazolium 4 with protected primary amines in the form of a phthalimido (phtal) group by N-alkylation reactions with N- (haloalkyl) phthalimides,
4 donde X" y n se han definido anteriormente en la transformación a) y el puente entre anillos imidazólicos queda definido por una longitud de cadena de n' eslabones que puede estar comprendida entre 1 y 3. transformar las sales 4, mediante reacciones de metalacion en presencia de acetato de paladio, para formar y aislar complejos bis(NHC) quelato 5 con una amina primaria protegida en forma de grupo ftalimido (ftal), en los que los ligandos carbeno se encuentran coordinados, preferente pero no excluyentemente, por su carbono 2,
4 where X " and n have been previously defined in transformation a) and the bridge between imidazole rings is defined by a chain length of n 'links that can be comprised between 1 and 3. transform salts 4, by means of metallation reactions in presence of palladium acetate, to form and isolate bis (NHC) chelate 5 complexes with a protected primary amine in the form of a phthalimide (phtal) group, in which the carbine ligands are coordinated, preferably but not exclusively, by their carbon 2 ,
5 donde X" y n se han definido anteriormente en la transformación a) y n' en la transformación g); y donde adicionalmente los ligandos X pueden independientemente ser un haluro, carboxilato, hidruro, o un alquilo, alilo, arilo, alquilarilo, alcóxido, arilóxido, beta-dicetonato, tiolato sustituidos o no sustituidos i) transformar los complejos quelato 5, por procedimientos convencionales de la síntesis de Gabriel (hidrólisis ácida o básica), o preferentemente por el método de Ing-Manske utilizando hidracina, para formar y aislar complejos bis(NHC) quelato de tipo lll(A) con grupos amina primaria terminal de cadena, en los que los ligandos carbeno se encuentran coordinados, preferente pero no excluyentemente, por su carbono 2, 5 where X " and n have been defined above in transformation a) and n 'in transformation g); and where additionally the X ligands can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate i) transform chelate complexes 5, by conventional methods of Gabriel's synthesis (acidic or basic hydrolysis), or preferably by Ing-Manske's method using hydrazine, to form and isolate bis (NHC) chelate complexes of type lll (A) with primary terminal chain amine groups, in which the carbine ligands are coordinated, preferably but not exclusively, by their carbon 2,
DESCRIPCIÓN DE LOS DIBUJOS DESCRIPTION OF THE DRAWINGS
Figura 1. Representación esquemática de la heterogeneización de los CPs objeto de la presente invención. Figure 1. Schematic representation of the heterogeneization of the CPs object of the present invention.
Figura 2. Representación esquemática de los CPs objeto de la presente invención.
Figura 3. Esquema de síntesis de los nuevos CPs de los tipos I, II y III y de sus precursores. MODO DE REALIZACIÓN DE LA INVENCIÓN Figure 2. Schematic representation of the CPs object of the present invention. Figure 3. Scheme of synthesis of the new CPs of types I, II and III and their precursors. EMBODIMENT OF THE INVENTION
La presente invención se ilustra adicionalmente con los siguientes ejemplos ilustrativos, aunque no limitantes, en los que se indican procedimientos experimentales, datos espectroscópicos y analíticos de complejos de paladio y de sus precursores. The present invention is further illustrated by the following illustrative, but not limiting, examples in which experimental procedures, spectroscopic and analytical data of palladium complexes and their precursors are indicated.
Ejemplo 1. Preparación de la sal de imidazolio 1.1. Example 1. Preparation of the imidazolium salt 1.1.
En una ampolla de 100 mL, dotada con una válvula de punzón de teflón, se colocó el N- metilimidazol (0,65 g, 7,8 mmol) y la N-(2-Bromoetil)ftalimida (1 ,00 g, 3,9 mmol), en unos 40 mL de THF y se calentó con agitación hasta 80 °C. Tras 16 h se observó la presencia de un precipitado blanco que, tras filtrar, se lavó con hexano (2 x 10 mL) para eliminar el exceso de N-metilimidazol y se secó a vacío. Se obtuvo el producto 1.1 como un sólido blanco (1 ,18 g, 90%). Anal. Cale, para Ci4H1402N3Br H20 (354,20): C, 47,47; H, 4,55; N, 1 1 ,86%. Encontrado: C, 47,42; H, 4,24; N, 1 1 ,93%. RMN 1 H (CDCI3, 300 MHz): 5 4,06 (s, 3H, Imz-Me), 4,23 (t, 3 H,H = 5,4 Hz, 2H, CH2ftal), 4,79 (t, 3 H,H = 5,4 Hz, 2H, CH2lmz), 7,25 y 7,26 (2 x s, 2 x 1 H, lmz-H4 y H5), 7,73 (m, 2H, o-ftal), 7,80 (m, 2H, m-ftal), 10,57 (s, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): 5 35,3 (CH2ftal), 37,5 (Imz-Me), 47,4 (CH2lmz), 122,4 y 123, 1 (Imz-C4 y C5), 122,7 (o-ftal), 131 ,0 (/pso-ftal), 134, 1 (m-ftal), 136,6 (Imz-C2), 167,2 (C=0). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 256, 1092 [M - Br]+. In a 100 mL ampoule, equipped with a Teflon punch valve, N-methylimidazole (0.65 g, 7.8 mmol) and N- (2-Bromoethyl) phthalimide (1,00 g, 3 , 9 mmol), in about 40 mL of THF and heated with stirring to 80 ° C. After 16 h the presence of a white precipitate was observed which, after filtering, was washed with hexane (2 x 10 mL) to remove excess N-methylimidazole and dried under vacuum. Product 1.1 was obtained as a white solid (1.18 g, 90%). Anal. Cale, for Ci 4 H 14 0 2 N 3 Br H 2 0 (354.20): C, 47.47; H, 4.55; N, 1 1, 86%. Found: C, 47.42; H, 4.24; N, 1 1, 93%. 1 H NMR (CDCI 3 , 300 MHz): 5 4.06 (s, 3H, Imz-Me), 4.23 (t, 3 H , H = 5.4 Hz, 2H, CH 2 ftal), 4, 79 (t, 3 H , H = 5.4 Hz, 2H, CH 2 lmz), 7.25 and 7.26 (2 xs, 2 x 1 H, lmz-H 4 and H 5 ), 7.73 ( m, 2H, o-ftal), 7.80 (m, 2H, m-ftal), 10.57 (s, 1 H, Imz-H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): 5 35.3 (CH 2 ftal), 37.5 (Imz-Me), 47.4 (CH 2 lmz), 122.4 and 123, 1 (Imz-C 4 and C 5 ), 122.7 (o-ftal), 131, 0 (/ pso-ftal), 134, 1 (m-ftal), 136.6 (Imz-C 2 ), 167, 2 (C = 0). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 256, 1092 [M-Br] + .
1.1 1.1
Ejemplo 2. Preparación de la sal de imidazolio 1.2. El compuesto 1.2 se preparó de forma similar a la descrita para la sal 1.1 del Ejemplo 1 , partiendo de N-mesitilimidazol (0,50 g, 2,7 mmol) y N-(2-bromoetil)ftalimida (0,34 g, 1 ,4 mmol), en THF (40 mL), a 90 °C y durante 16 h. Se obtuvo el compuesto 1.2 como un
sólido aceitado de color blanco (0,56 g, 95%). Anal. Cale, para C22H2202N3Br (440,34): C, 60,01 ; H, 5,04; N, 9,54%. Encontrado: C, 59,75; H, 5,06; N, 9,47%. RMN 1 H (CDCI3, 300 MHz): δ 2,09 (s, 6H, Mes- o- Me), 2,31 (s, 3H, Mes-p-Me), 4,33 (t, 3 H,H = 5,0 Hz, 2H, CH2ftal), 5, 14 (t, 3 H,H = 5,0 Hz, 2H, CH2lmz), 6,97 (s, 2H, m-Mes), 7,04 y 7,51 (2 x t, 3JH,H = 1 ,9 Hz, 2 x 1 H, Imz-H4 y H5), 7,73 (m, 2H, o-ftal), 7,78 (m, 2H, m-ftal), 10,50 (t, 3JH,H = 1 ,9 Hz, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 17,6 (Mes-p-Me), □□□□ (Mes-o- Me), 39,0 (CH2ftal), 49,6 (CH2lmz), 122,8 y 123,0 (Imz-C4 y C5), 123,7 (o-ftal), 129,9 (m- Mes), 130,6 (/pso-Mes), 131 ,5 (/pso-ftal), 134,4 (o-Mes), 134,5 (m-ftal), 138,8 (Imz-C2), 141 ,4 (p-Mes), 167,2 (C=0). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 360,171 1 [M - Br]+. Example 2. Preparation of the imidazolium salt 1.2. Compound 1.2 was prepared similarly to that described for salt 1.1 of Example 1, starting from N-mesitylimidazole (0.50 g, 2.7 mmol) and N- (2-bromoethyl) phthalimide (0.34 g, 1.4 mmol), in THF (40 mL), at 90 ° C and for 16 h. Compound 1.2 was obtained as a white oiled solid (0.56 g, 95%). Anal. Cale, for C 22 H 22 0 2 N 3 Br (440.34): C, 60.01; H, 5.04; N, 9.54%. Found: C, 59.75; H, 5.06; N, 9.47%. 1 H NMR (CDCI 3 , 300 MHz): δ 2.09 (s, 6H, Mes-o-Me), 2.31 (s, 3H, Month-p-Me), 4.33 (t, 3 H , H = 5.0 Hz, 2H, CH 2 ftal), 5, 14 (t, 3 H , H = 5.0 Hz, 2H, CH 2 lmz), 6.97 (s, 2H, m-Month) , 7.04 and 7.51 (2 xt, 3 J H, H = 1, 9 Hz, 2 x 1 H, Imz-H 4 and H 5 ), 7.73 (m, 2H, o-ftal), 7.78 (m, 2H, m-ftal), 10.50 (t, 3 J H, H = 1, 9 Hz, 1 H, Imz-H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 17.6 (Month-p-Me), □□□□ (Month-o-Me), 39.0 (CH 2 ftal), 49, 6 (CH 2 lmz), 122.8 and 123.0 (Imz-C 4 and C 5 ), 123.7 (o-ftal), 129.9 (m-Month), 130.6 (/ pso-Month ), 131.5 (/ pso-ftal), 134.4 (o-Month), 134.5 (m-ftal), 138.8 (Imz-C 2 ), 141, 4 (p-Month), 167 , 2 (C = 0). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 360,171 1 [M-Br] + .
1.2 1.2
Ejemplo 3. Preparación de la sal de imidazolio 1.3. Example 3. Preparation of the imidazolium salt 1.3.
El compuesto 1.3 se preparó de forma similar a la descrita para la sal 1.1 del Ejemplo 1 , partiendo de N-(2,6-diisopropilfenil)imidazol (0,50 g, 2,2 mmol) y N-(2-bromoetil)ftalimida (0,28 g, 1 , 1 mmol), en THF (40 mL), a 90 °C y durante 16 h. Se obtuvo el compuesto 1.3 como un sólido blanco aceitoso (0,48 g, 90%). Anal. Cale, para C25H2802N3Br- 1 ,2H20 (505,04): C, 59,57; H, 6,08; N, 8,34%. Encontrado: C, 59,96; H, 5,95; N, 7,92%. RMN 1 H (CDCIs, 300 MHz): δ 1 , 1 1 (d, 3 H,H = 7,0 Hz, 6H, CH(CH3)2), 1 ,23 (d, 3JH,H = 7,0 Hz, 6H, CH(CH3)2), 1 ,83 (sep, 3JH,H = 7,0 Hz, 2H, CH(CH3)2), 4,35 (t, 3JH,H = 5,2 Hz, 2H, CH2ftal), 5,22 (t, 3JH,H = 5,2 Hz, 2H, CH2lmz), 7,03 y 7,58 (2 x s, 2 χ 1 H, Imz-H4 y H5), 7,04 (d, 3JH,H = 7,9 Hz, 2H, m-Ph), 7,51 (t, 3JH,H = 7,9 Hz, 1 H, p-Ph), 7,73 (m, 2H, o-ftal), 7,80 (m, 2H, m-ftal), 10,51 (s ancho, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): 5 24,3 (CH(CH3)2), □□□□□( CH(CH3)2), 28,5 (CH(CH3)2), 39,2 (CH2ftal), 49,7 (CH2lmz), 123,0 y 123,8 (Imz- C4 y C5), 123,6 (m-Ph), 124,7 (o-ftal), 130,1 (/pso-Ph), 131 ,6 (/pso-ftal), 131 ,9 (o-Ph), 134,5 (m-ftal), 138,9 (Imz-C2), 145,5 (p-Ph), 167,7 (C=0). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 402,2176 [M - Br]+.
Compound 1.3 was prepared similarly to that described for salt 1.1 of Example 1, starting with N- (2,6-diisopropylphenyl) imidazole (0.50 g, 2.2 mmol) and N- (2-bromoethyl) Phthalimide (0.28 g, 1.1 mmol), in THF (40 mL), at 90 ° C and for 16 h. Compound 1.3 was obtained as an oily white solid (0.48 g, 90%). Anal. Cale, for C 25 H 28 0 2 N 3 Br- 1, 2H 2 0 (505.04): C, 59.57; H, 6.08; N, 8.34%. Found: C, 59.96; H, 5.95; N, 7.92%. 1 H NMR (CDCIs, 300 MHz): δ 1, 1 1 (d, 3 H , H = 7.0 Hz, 6H, CH (CH 3 ) 2 ), 1, 23 (d, 3 J H , H = 7.0 Hz, 6H, CH (CH 3 ) 2 ), 1, 83 (Sep, 3 J H , H = 7.0 Hz, 2H, CH (CH 3 ) 2 ), 4.35 (t, 3 J H , H = 5.2 Hz, 2H, CH 2 ftal), 5.22 (t, 3 J H , H = 5.2 Hz, 2H, CH 2 lmz), 7.03 and 7.58 (2 xs , 2 χ 1 H, Imz-H 4 and H 5 ), 7.04 (d, 3 J H , H = 7.9 Hz, 2H, m-Ph), 7.51 (t, 3 J H , H = 7.9 Hz, 1 H, p-Ph), 7.73 (m, 2H, o-ftal), 7.80 (m, 2H, m-ftal), 10.51 (wide s, 1 H, Imz-H 2 ). 13 C NMR { 1 H} (CDCI 3 , 75 MHz): 5 24.3 (CH (CH 3 ) 2 ), □□□□□ (CH (CH 3 ) 2 ), 28.5 (CH (CH 3 ) 2 ), 39.2 (CH 2 ftal), 49.7 (CH 2 lmz), 123.0 and 123.8 (Imz-C 4 and C 5 ), 123.6 (m-Ph), 124, 7 (o-ftal), 130.1 (/ pso-Ph), 131, 6 (/ pso-ftal), 131, 9 (o-Ph), 134.5 (m-ftal), 138.9 (Imz -C 2 ), 145.5 (p-Ph), 167.7 (C = 0). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 402.2176 [M-Br] + .
Ejemplo 4. Preparación de la sal de imidazolio 2(Si)1. En una ampolla de 50 mL con (3-bromopropil)trietoxisilano (0,29 g, 1 ,0 mmol), se hizo vacío durante 10 min y se añadieron 2 mL de CH3CN seco. A continuación se adicionó el N-metilimidazol (0,08 g, 1 ,0 mmol). La disolución amarilla resultante se dejó con agitación a 100 °C durante 16 h, para después evaporar el disolvente. El aceite amarillo resultante se lavó con hexano (2 x 15 mL), obteniéndose el compuesto 2(Si)1 como un aceite amarillo (0,33 g, 89%). Anal. Cale, para Ci3H2703N2SiBr (367,36): C, 42,50; H, 7,41 ; N, 7,62%. Encontrado: C, 42,00; H, 6,85; N, 8,04%. RMN 1 H (CDCI3, 300 MHz): δ 0,52 (t, 3JH,h = 8,5 Hz, 2H, SiCH2), 1 , 12 (t, 3 H,H = 7,0 Hz, 9H, CH3CH20), 1 ,93 (m, 2H, S¡CH2CH2), 3,72 (c, 3JH,H = 7,0 Hz, 6H, CH3CH20), 4,04 (s, 3H, Imz-Me), 4,24 (t, 3 H,H = 7,2 Hz, 2H, CH2lmz), 7,31 y 7,57 (2 x t, 3JH,H = 1 ,6 HZ, 2 χ 1 H, Imz-H4 y H5), 10,2 (s, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 7,0 (SiCH2), 18,2 (CH3CH20), 24,3 (SiCH2CH2), 36,6 (Imz-Me), 51 ,6 (CH2lmz), 58,5 (CH3CH20), 121 ,7 y 123,5 (Imz-C4 y C5), 137,4 (Imz-C2). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 247,1780 [M - Br]+.
Example 4. Preparation of the imidazolium salt 2 (Si) 1. In a 50 mL ampoule with (3-bromopropyl) triethoxysilane (0.29 g, 1.0 mmol), it was emptied for 10 min and 2 mL of dry CH 3 CN was added. The N-methylimidazole (0.08 g, 1.0 mmol) was then added. The resulting yellow solution was left under stirring at 100 ° C for 16 h, then the solvent was evaporated. The resulting yellow oil was washed with hexane (2 x 15 mL), obtaining compound 2 (Si) 1 as a yellow oil (0.33 g, 89%). Anal. Cale, for Ci 3 H 27 0 3 N 2 SiBr (367.36): C, 42.50; H, 7.41; N, 7.62%. Found: C, 42.00; H, 6.85; N, 8.04%. 1 H NMR (CDCI 3 , 300 MHz): δ 0.52 (t, 3 JH , h = 8.5 Hz, 2H, SiCH 2 ), 1, 12 (t, 3 H , H = 7.0 Hz, 9H, CH 3 CH 2 0), 1, 93 (m, 2H, S¡CH 2 CH 2 ), 3.72 (c, 3 J H , H = 7.0 Hz, 6H, CH 3 CH 2 0) , 4.04 (s, 3H, Imz-Me), 4.24 (t, 3 H , H = 7.2 Hz, 2H, CH 2 lmz), 7.31 and 7.57 (2 xt, 3 J H , H = 1, 6 HZ, 2 χ 1 H, Imz-H 4 and H 5 ), 10.2 (s, 1 H, Imz-H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 7.0 (SiCH 2 ), 18.2 (CH 3 CH 2 0), 24.3 (SiCH 2 CH 2 ), 36.6 (Imz -Me), 51, 6 (CH 2 lmz), 58.5 (CH 3 CH 2 0), 121, 7 and 123.5 (Imz-C 4 and C 5 ), 137.4 (Imz-C 2 ) . MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 247.1780 [M-Br] + .
Br~ Br ~
2(Si)1 2 (Yes) 1
Ejemplo 5. Preparación de la sal de imidazolio 2(Si)2. Example 5. Preparation of the imidazolium salt 2 (Si) 2.
El compuesto 2(Si)2 se preparó de forma similar a la descrita para la sal 2(Si)1 del Ejemplo 4, partiendo de N-mesitilimidazol (0,22 g, 1 ,2 mmol) y el derivado bromado (0,34 g, 1 ,2 mmol), en CH3CN (2,5 mL), a 100 °C y durante 24 h. Todos los reactivos sólidos se mantuvieron previamente a vacío durante 10 min. Se obtuvo el compuesto 2(Si)2 como un sólido blanco aceitado (0,55 g, 98%). Anal. Cale, para C2i H35O3N2SiBr 0, 1 H2O (489,530): C, 53,29; H, 7,50; N, 5,92%. Encontrado: C, 52,77; H, 7, 12; N, 6,46%. RMN 1 H (CDCI3, 300 MHz): 5 0,62 (m, 2H, SiCH2), 1 , 18 (t, 3JH,H = 7,0 Hz, 9H, CH3CH20), 2,04 (s,
6H, Mes-o-Me), 2,07 (m, 2H, SiCH2CH2), 2,30 (s, 3H, Mes-p-Me), 3,80 (c, 3 H,H = 7,0 Hz, 6H, CH3CH20), 4,72 (t, 3 H,H = 7,0 Hz, 2H, CH2lmz), 6,96 (s, 2H, m-Mes), 7, 15 y 7,67 (2 x t, 3JH,H = 1 ,5 HZ, 2 X 1 H, Imz-H4 y H5), 10,4 (s ancho, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 6,8 (SiCH2), 17,6 (Mes-o-Me), 18,2 (CH3CH20), 21 ,0 (Mes-p-Me), 24,5 (SiCH2CH2), 52,0 (CH2lmz), 58,6 (CH3CH20), 122,7 y 122,9 (Imz-C4 y C5), 129,8 (m-Mes), 130,6 (/pso-Mes), 134,1 (o-Mes), 138,2 (Imz-C4), 141 ,2 (p-Mes). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 391 ,2412 [M - Br]+. Compound 2 (Si) 2 was prepared similarly to that described for salt 2 (Si) 1 of Example 4, starting from N-mesitylimidazole (0.22 g, 1.2 mmol) and the brominated derivative (0, 34 g, 1.2 mmol), in CH 3 CN (2.5 mL), at 100 ° C and for 24 h. All solid reagents were previously kept under vacuum for 10 min. Compound 2 (Si) 2 was obtained as an oiled white solid (0.55 g, 98%). Anal. Cale, for C 2 i H 35 O 3 N 2 SiBr 0, 1 H 2 O (489,530): C, 53.29; H, 7.50; N, 5.92%. Found: C, 52.77; H, 7, 12; N, 6.46%. 1 H NMR (CDCI 3 , 300 MHz): 5 0.62 (m, 2H, SiCH 2 ), 1, 18 (t, 3 J H , H = 7.0 Hz, 9H, CH 3 CH 2 0), 2.04 (s, 6H, Month-o-Me), 2.07 (m, 2H, SiCH 2 CH 2 ), 2.30 (s, 3H, Month-p-Me), 3.80 (c, 3 H, H = 7 , 0 Hz, 6H, CH 3 CH 2 0), 4.72 (t, 3 H, H = 7.0 Hz, 2H, CH 2 lmz), 6.96 (s, 2H, m-Month), 7 , 15 and 7.67 (2 xt, 3 J H, H = 1, 5 HZ, 2 X 1 H, Imz-H 4 and H 5 ), 10.4 (wide s, 1 H, Imz-H 2 ) . 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 6.8 (SiCH 2 ), 17.6 (Month-o-Me), 18.2 (CH 3 CH 2 0), 21, 0 ( Month-p-Me), 24.5 (SiCH 2 CH 2 ), 52.0 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 122.7 and 122.9 (Imz-C 4 and C 5 ), 129.8 (m-Month), 130.6 (/ pso-Month), 134.1 (o-Month), 138.2 (Imz-C 4 ), 141, 2 (p-Month) . MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 391, 2412 [M-Br] + .
2(Si)2 2 (Yes) 2
Ejemplo 6. Preparación de la sal de imidazolio 2(Si)3. Example 6. Preparation of the imidazolium salt 2 (Si) 3.
El compuesto 2(Si)3 se preparó de forma similar a la descrita para la sal 2(Si)1 del Ejemplo 4, partiendo de N-(2,6-diisopropilfenil)imidazol (0,28 g, 1 ,2 mmol) y el derivado bromado (0,34 g, 1 ,2 mmol), en CH3CN (2,5 mL), a 100 °C y durante 24 h. Todos los reactivos sólidos se tuvieron a vacío durante 10 min antes de su utilización. Se obtuvo el compuesto 2(Si)3 como un sólido blanco de aspecto aceitoso (0,61 g, 99%). Anal. Cale, para C24H4103N2SiBr (2,4CH3CN y 2C3H60) (728,28): C, 57,52; H, 8,03; N, 7,62%. Encontrado: C, 57,91 ; H, 8,03; N, 7,27%. RMN 1 H (CDCI3, 300 MHz): 5 0,61 (t, 3JH,H = 7,7 Hz, 2H, SiCH2), 1 , 13 (d, 3JH,H = 7,2 Hz, 6H, CH(CH3)2), 1 , 18 (t, 3JH,H = 7,0 Hz, 9H, CH3CH20), 1 ,20 (d, 3JH,H = 7,2 Hz, 6H, CH(CH3)2) , 2,07 (m, 3JH,H = 7,7 Hz, 2H SiCH2CH2), 2,25 (sep, 3JH,H = 7,2 Hz, 6H, CH(CH3)2), 3,78 (c, 3 H,H = 7,0 Hz, 6H, CH3CH20), 4,78 (t, 3JH,H = 7,7 Hz, 2H, CH2lmz), 7, 18 y 7,88 ( 2 x s ancho, 2 χ 1 H, Imz-H4 y H5), 7,27 (d, 2H, 3JH,H = 7,6 Hz, m-Ph), 7,49 (t, 1 H, 3JH,H = 7,6 Hz, p-Ph), 10,3 (s, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 6,6 (SiCH2), 18,2 (CH3CH20), 24,0 (CH(CH3)2), 24,3 (CH(CH3)2), 24,5 (SiCH2CH2), 28,6 (CH(CH3)2), 52,0 (CH2lmz), 58,5 (CH3CH20), 123,0 y 124,0 (Imz-C4 y C5), 124,6 (m-Ph), 130,0 (/pso-Ph), 131 ,8 (C6H3(o-Ph), 138,2 (Imz-C2), 145,2 (p-Ph). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 433,2881 [M - Br]+.
Compound 2 (Si) 3 was prepared similarly to that described for salt 2 (Si) 1 of Example 4, starting from N- (2,6-diisopropylphenyl) imidazole (0.28 g, 1.2 mmol) and the brominated derivative (0.34 g, 1.2 mmol), in CH 3 CN (2.5 mL), at 100 ° C and for 24 h. All solid reagents were held in vacuo for 10 min before use. Compound 2 (Si) 3 was obtained as a white solid of oily appearance (0.61 g, 99%). Anal. Cale, for C 24 H 41 0 3 N 2 SiBr (2.4CH 3 CN and 2C 3 H 6 0) (728.28): C, 57.52; H, 8.03; N, 7.62%. Found: C, 57.91; H, 8.03; N, 7.27%. 1 H NMR (CDCI 3 , 300 MHz): 5 0.61 (t, 3 J H, H = 7.7 Hz, 2H, SiCH 2 ), 1, 13 (d, 3 J H, H = 7.2 Hz, 6H, CH (CH 3 ) 2 ), 1, 18 (t, 3 J H, H = 7.0 Hz, 9H, CH 3 CH 2 0), 1, 20 (d, 3 J H, H = 7.2 Hz, 6H, CH (CH 3 ) 2 ), 2.07 (m, 3 J H, H = 7.7 Hz, 2H SiCH 2 CH 2 ), 2.25 (Sep, 3 J H , H = 7.2 Hz, 6H, CH (CH 3 ) 2 ), 3.78 (c, 3 H , H = 7.0 Hz, 6H, CH 3 CH 2 0), 4.78 (t, 3 J H , H = 7.7 Hz, 2H, CH 2 lmz), 7, 18 and 7.88 (2 xs wide, 2 χ 1 H, Imz-H 4 and H 5 ), 7.27 (d, 2H, 3 J H, H = 7.6 Hz , m-Ph), 7.49 (t, 1 H, 3 J H, H = 7.6 Hz , p-Ph), 10.3 (s, 1 H, Imz -H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 6.6 (SiCH 2 ), 18.2 (CH 3 CH 2 0), 24.0 (CH (CH 3 ) 2 ), 24.3 (CH (CH 3 ) 2 ), 24.5 (SiCH 2 CH 2 ), 28.6 (CH (CH 3 ) 2 ), 52.0 (CH 2 lmz), 58.5 (CH 3 CH 2 0) , 123.0 and 124.0 (Imz-C 4 and C 5 ), 124.6 (m-Ph), 130.0 (/ pso-Ph), 131, 8 (C 6 H 3 (o-Ph) , 138.2 (Imz-C 2 ), 145.2 (p-Ph) MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 433.2881 [M-Br] + .
Ejemplo 7. Preparación de la sal de imidazolio 2(A)1. Se adicionó hidrazina (2, 10 ml_, 43, 1 mmol) a una ampolla de 50 ml_ con la sal de imidazolio 1.1 descrita en el Ejemplo 1 (1 ,40 g, 4,3 mmol) en 25 ml_ de 2-propanol y se calentó a 40 °C durante una noche. La suspensión blanca inicial se tornó a una disolución transparente con el avance de la reacción para finalmente, precipitar un sólido blanco que se corresponde con el subproducto de la desprotección, la ftalilhidrazina. La mezcla se enfrió, filtró y evaporó obteniéndose el producto deseado 2(A)1 como un aceite amarillo (0,80 g, 95%). Anal. Cale, para C6H12N3Br (206,08): C, 34,97; H, 5,87; N, 20,39%; Encontrado: C, 34,31 ; H, 5,98; N, 19,89%. RMN 1 H (CDCI3, 300 MHz): 5 3, 19 (t, 3 H,H = 5,6 Hz, 2H, NH2CH2), 4,05 (s, 3H, Imz-Me), 4,44 (t, 3 H,H = 5,6 Hz, 2H, CH2lmz), 7,27 y 7,49 (2 x s, 2 x 1 H, Imz-H4 y H5), 10,33 (s, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 36,7 (NH2CH2), 41 ,4 (Imz-Me), 52,3 (CH2lmz), 122,3 y 122,5 (Imz-C4 y C5), 138,6 (Imz- C2). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 126,1026 [M - Br]+.
Example 7. Preparation of the imidazolium salt 2 (A) 1. Hydrazine (2.10 ml_, 43.1 mmol) was added to a 50 ml vial with the imidazolium salt 1.1 described in Example 1 (1.40 g, 4.3 mmol) in 25 ml_ of 2-propanol and It was heated at 40 ° C overnight. The initial white suspension was returned to a clear solution with the progress of the reaction to finally precipitate a white solid that corresponds to the by-product of the deprotection, phthalylhydrazine. The mixture was cooled, filtered and evaporated to obtain the desired product 2 (A) 1 as a yellow oil (0.80 g, 95%). Anal. Cale, for C 6 H 12 N 3 Br (206.08): C, 34.97; H, 5.87; N, 20.39%; Found: C, 34.31; H, 5.98; N, 19.89%. 1 H NMR (CDCI 3 , 300 MHz): 5 3, 19 (t, 3 H , H = 5.6 Hz, 2H, NH 2 CH 2 ), 4.05 (s, 3H, Imz-Me), 4 , 44 (t, 3 H , H = 5.6 Hz, 2H, CH 2 lmz), 7.27 and 7.49 (2 xs, 2 x 1 H, Imz-H 4 and H 5 ), 10.33 (s, 1 H, Imz-H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 36.7 (NH 2 CH 2 ), 41, 4 (Imz-Me), 52.3 (CH 2 lmz), 122.3 and 122, 5 (Imz-C 4 and C 5 ), 138.6 (Imz-C 2 ). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 126.1026 [M-Br] + .
2(A)1 2 (A) 1
Ejemplo 8. Preparación de la sal de imidazolio 2(A)2. Example 8. Preparation of the imidazolium salt 2 (A) 2.
El compuesto 2(A)2 se preparó de forma similar a la descrita para la sal 2(A)1 del Ejemplo 7, partiendo de la sal de imidazolio 1.2 descrita en el Ejemplo 2 (1 ,29 g, 2,9 mmol) e hidrazina (1 ,43 mL, 29,0 mmol), en isopropanol, a 40 °C y durante una noche. Tras filtrar, evaporar y lavar con hexano se obtuvo la sal de imidazolio 2(A)2 como un aceite amarillo (0,87 g, 95%). Anal. Cale, para C14H20N3Br 0,7H2O (322,84): C, 52,08; H, 6,68; N, 13,02%; Encontrado: C, 51 ,82; H, 6,34; N, 13,24%. RMN 1 H (CDCI3, 300 MHz): δ 2,05 (s, 6H, Mes-o-Me), 2,31 (s, 3H, Mes-p-Me), 3,23 (t, 3JH,H = 5,6 Hz, 2H, NH2CH2), 4,81 (t, 3JH,H = 5,6 Hz, 2H, CH2lmz), 6,97 (s, 2H, m-Mes), 7, 1 1 y 7,91 (2 x t, 3JH,H = 1 ,7 Hz, 2 x
1 H, Imz-H4 y H5), 10,09 (t, 3 H,H = 1 ,7 Hz, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 17,8 (Mes-p-Me), 21 ,0 (Mes-o-Me), 40,9 (NH2CH2), 50,3 (CH2lmz), 123,0 y 124,0 (Imz-C4 y C5), 129,7 (m-Mes), 130,7 (/pso-Mes), 134,4 (o-Mes), 137,9 (Imz-C2), 141 ,0 (p-Mes). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 230,1652 [M - Br]+. Compound 2 (A) 2 was prepared similarly to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1.2 described in Example 2 (1.29 g, 2.9 mmol) and hydrazine (1.43 mL, 29.0 mmol), in isopropanol, at 40 ° C and overnight. After filtering, evaporating and washing with hexane, the imidazolium 2 (A) 2 salt was obtained as a yellow oil (0.87 g, 95%). Anal. Cale, for C 14 H 20 N 3 Br 0.7H 2 O (322.84): C, 52.08; H, 6.68; N, 13.02%; Found: C, 51, 82; H, 6.34; N, 13.24%. 1 H NMR (CDCI 3 , 300 MHz): δ 2.05 (s, 6H, Month-o-Me), 2.31 (s, 3H, Month-p-Me), 3.23 (t, 3 J H , H = 5.6 Hz, 2H, NH 2 CH 2 ), 4.81 (t, 3 J H , H = 5.6 Hz, 2H, CH 2 lmz), 6.97 (s, 2H, m -Month), 7, 1 1 and 7.91 (2 xt, 3 J H , H = 1, 7 Hz, 2 x 1 H, Imz-H 4 and H 5 ), 10.09 (t, 3 H , H = 1, 7 Hz, 1 H, Imz-H 2 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 17.8 (Month-p-Me), 21, 0 (Month-o-Me), 40.9 (NH 2 CH 2 ), 50, 3 (CH 2 lmz), 123.0 and 124.0 (Imz-C 4 and C 5 ), 129.7 (m-Month), 130.7 (/ pso-Month), 134.4 (o-Month ), 137.9 (Imz-C 2 ), 141, 0 (p-Month). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 230.1652 [M-Br] + .
2(A)2 2 (A) 2
Ejemplo 9. Preparación de la sal de imidazolio 2(A)3. El compuesto 2(A)3 se preparó de forma similar a la descrita para la sal 2(A)1 del Ejemplo 7, partiendo de la sal de imidazolio 1.3 descrita en el Ejemplo 3 (0,46 ml_, 9,50 mmol) e hidrazina (0,46 ml_, 9,50 mmol), en isopropanol, a 40 °C y durante una noche. Tras filtrar, evaporar y lavar con hexano se obtuvo la sal de imidazolio 2(A)2 como un aceite amarillo (0,31 g, 92%). Anal. Cale, para C17H26N3Br 0,4H2O: C, 56,79; H, 7,51 ; N, 1 1 ,69%; Encontrado: C, 57,07; H, 7,98; N, 12,13%. RMN 1 H (CDCI3, 300 MHz): 5 1 , 17 (d, 3JH,H = 6,9 Hz, 12H, CH(CH3)2), 2,31 (sep., 3 H,H = 6,9 Hz, 2H, CH(CH3)2), 3,22 (t, 3JH,H = 5,4 Hz, 2H, NH2CH2), 4,87 (t, 3JH,H = 5,4 Hz, 2H, CH2lmz), 7, 12 y 7,58 (2 x t, 3JH,H = 1 ,3 Hz, 2 x 1 H, Imz-H4 y H5), 7,28 (d, 3JH,H = 7,9 Hz, 2H, m-Ph), 7,52 (t, 3JH,H = 7,9 Hz, 1 H, p- Ph), 10,51 (t, 3JH,H = 1 ,3 Hz, 1 H, Imz-H2). RMN 13C{1 H} (CDCI3, 75 MHz): δ 24, 1 (CH(CH3)2), 24,4 (CH(CH3)2), 28,6 (CH(CH3)2), 41 ,6 (NH2CH2), 51 ,6 (CH2lmz), 123,2 y 123,5 (Imz-C4 y C5), 124,7 (m-Ph), 130,1 (/pso-Ph), 131 ,9 (o-Ph), 139,0 (Imz-C2), 145,5 (p-Ph). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 272,2082 [M - Br]+. Example 9. Preparation of the imidazolium salt 2 (A) 3. Compound 2 (A) 3 was prepared similarly to that described for salt 2 (A) 1 of Example 7, starting from imidazolium salt 1.3 described in Example 3 (0.46 ml_, 9.50 mmol) and hydrazine (0.46 ml_, 9.50 mmol), in isopropanol, at 40 ° C and overnight. After filtering, evaporating and washing with hexane, the imidazolium 2 (A) 2 salt was obtained as a yellow oil (0.31 g, 92%). Anal. Cale, for C 17 H 26 N 3 Br 0.4H 2 O: C, 56.79; H, 7.51; N, 1 1, 69%; Found: C, 57.07; H, 7.98; N, 12.13%. 1 H NMR (CDCI 3 , 300 MHz): 5 1, 17 (d, 3 J H , H = 6.9 Hz, 12H, CH (CH 3 ) 2 ), 2.31 (Sep., 3 H , H = 6.9 Hz, 2H, CH (CH 3 ) 2 ), 3.22 (t, 3 J H , H = 5.4 Hz, 2H, NH 2 CH 2 ), 4.87 (t, 3 J H , H = 5.4 Hz, 2H, CH 2 lmz), 7, 12 and 7.58 (2 xt, 3 J H , H = 1, 3 Hz, 2 x 1 H, Imz-H 4 and H 5 ) , 7.28 (d, 3 J H , H = 7.9 Hz, 2H, m-Ph), 7.52 (t, 3 J H , H = 7.9 Hz, 1 H, p- Ph), 10.51 (t, 3 J H , H = 1.3 Hz, 1 H, Imz-H 2 ). 13 C NMR { 1 H} (CDCI 3 , 75 MHz): δ 24, 1 (CH (CH 3 ) 2 ), 24.4 (CH (CH 3 ) 2 ), 28.6 (CH (CH 3 ) 2 ), 41, 6 (NH 2 CH 2 ), 51, 6 (CH 2 lmz), 123.2 and 123.5 (Imz-C 4 and C 5 ), 124.7 (m-Ph), 130.1 (/ pso-Ph), 131, 9 (o-Ph), 139.0 (Imz-C 2 ), 145.5 (p-Ph). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 272,2082 [M-Br] + .
Ejemplo 10. Preparación del complejo de paladio l(Si)1. Example 10. Preparation of palladium complex l (Si) 1.
Se pesaron en una ampolla bajo argón la sal de imidazolio 2(Si)1 descrita en el Ejemplo 4 (0,58 g, 1 ,6 mmol), cloruro de paladio (0,28 g, 1 ,6 mmol), carbonato de potasio (1 ,09 g,
7,9 mmol) y yoduro de sodio (1 ,66 g, 1 1 , 1 mmol), y se pusieron en un desecador Büchi a 10 mbar y 95 °C durante 24 h. Posteriormente, se añadieron 12 ml_ de 4-picolina, tratada previamente con moléculas shieves durante una noche, formándose una suspensión rojiza que se dejó agitando a 80 °C durante 24 h bajo argón. Tras evaporar la 4-picolina, se extrajo con CHCI3, se filtró la disolución y se añadió hexano para eliminar restos de haluro de paladio. Tras filtrar y evaporar el disolvente se obtuvo el complejo 1 (Si)l como un sólido pulverulento de color amarillo (1 , 12 g, 96%). Anal. Cale, para Ci9H3303N3l2SiPd (739,80): C, 30,85; H, 4,50; N, 5,68%. Encontrado: C, 30,36; H, 4,40; N, 5,93%. RMN 1 H (CDCIs, 300 MHz): δ 0,73 (t, 3 H,H = 8,0 Hz, 2H, SiCH2), 1 ,21 (t, 3 H,H = 7,0 Hz, 9H, CH3CH2O), 2, 15 (m, 2H, S¡CH2CH2), 2,35 (s, 3H, pic-Me), 3,83 (c, 3JH,H = 7,0 Hz, 6H, CH3CH20), 3,95 (s, 3H, Imz-Me), 4,38 (t, 3JH,H = 8,0 Hz, 2H, CH2lmz), 6,90 y 6,96 (2 x d, 3JH,H = 2,0 Hz, 2 x 1 H, Imz-H4 y H5), 7,09 (d, 3JH,H = 5,9 Hz, 1 H, m-pic), 8,83 (d, 3JH,H = 5,9 Hz, 1 H, o-pic). RMN 13C{1 H} (CDCI3, 75 MHz): 5 7,7 (SiCH2), 18,4 (CH3CH20), 21 , 1 (pic- Me), 23, 1 (SiCH2CH2), 39,2 (Imz-Me), 53,7 (CH2lmz), 58,6 (CH3CH20), 121 ,7 y 123,0 (Imz-C4 y C5), 125,3 (m-pic), 145,6 (Imz-C2), 149,4 (p-pic), 153,2 (o-pic). IR (KBr): v 3050- 3120 (m, Csp-H st), 1618 (m, C=C st), 1542 (s, C=N st), 1420-1470 (m, arC=C st), 1080 (w, Si-O-C st), 957 (w, Si-O-C st), 806 (m, Si-C st), 687 errf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 740,9418 [M + H]+. The imidazolium 2 (Si) 1 salt described in Example 4 (0.58 g, 1.6 mmol), palladium chloride (0.28 g, 1.6 mmol), carbonate potassium (1, 09 g, 7.9 mmol) and sodium iodide (1.66 g, 11.1 mmol), and placed in a Büchi desiccator at 10 mbar and 95 ° C for 24 h. Subsequently, 12 ml_ of 4-picoline, previously treated with shieves molecules was added overnight, forming a reddish suspension that was allowed to stir at 80 ° C for 24 h under argon. After evaporating the 4-picoline, it was extracted with CHCI 3 , the solution was filtered and hexane was added to remove palladium halide residues. After filtering and evaporating the solvent, complex 1 (Si) 1 was obtained as a yellow powdery solid (1.12 g, 96%). Anal. Cale, for Ci 9 H 33 0 3 N 3 l 2 SiPd (739.80): C, 30.85; H, 4.50; N, 5.68%. Found: C, 30.36; H, 4.40; N, 5.93%. 1 H NMR (CDCIs, 300 MHz): δ 0.73 (t, 3 H , H = 8.0 Hz, 2H, SiCH 2 ), 1, 21 (t, 3 H , H = 7.0 Hz, 9H , CH3CH2O), 2, 15 (m, 2H, S¡CH 2 CH 2 ), 2.35 (s, 3H, pic-Me), 3.83 (c, 3 J H, H = 7.0 Hz, 6H, CH 3 CH 2 0), 3.95 (s, 3H, Imz-Me), 4.38 (t, 3 J H, H = 8.0 Hz, 2H, CH 2 lmz), 6.90 and 6.96 (2 xd, 3 J H, H = 2.0 Hz, 2 x 1 H, Imz-H 4 and H 5 ), 7.09 (d, 3 J H, H = 5.9 Hz, 1 H, m-pic), 8.83 (d, 3 J H, H = 5.9 Hz, 1 H, o-pic). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): 5 7.7 (SiCH 2 ), 18.4 (CH 3 CH 2 0), 21, 1 (pic-Me), 23, 1 (SiCH 2 CH 2 ), 39.2 (Imz-Me), 53.7 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 121, 7 and 123.0 (Imz-C 4 and C 5 ), 125.3 (m-pic), 145.6 (Imz-C 2 ), 149.4 (p-pic), 153.2 (o-pic). IR (KBr): v 3050-3120 (m, Csp-H st), 1618 (m, C = C st), 1542 (s, C = N st), 1420-1470 (m, arC = C st), 1080 (w, Si-OC st), 957 (w, Si-OC st), 806 (m, Si-C st), 687 errf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 740.9418 [M + H] + .
l(S¡)1 l (Yes) 1
Ejemplo 11. Preparación del complejo de paladio l(Si)2. Example 11. Preparation of the palladium complex l (Si) 2.
El compuesto l(Si)2 se preparó como se ha descrito para el complejo l(Si)1 del Ejemplo 10, partiendo de la sal de imidazolio 2(Si)2 descrita en el Ejemplo 5 (0,57 g, 1 ,2 mmol), cloruro de paladio (0,21 g, 1 ,2 mmol), carbonato de potasio (0,83 g, 6,0 mmol) y yoduro de sodio (1 ,26 g, 8,4 mmol), en 12 ml_ de 4-picolina, a 100 °C y durante 16 h. Se obtuvo el compuesto l(Si)2 como un sólido pulverulento de color naranja (0,99 g, 98%). Anal. Cale, para C27H4103N3l2SiPd (843,95): C, 38,43; H, 4,90; N, 4,98%. Encontrado: C, 38,22; H, 4,78; N, 5,36%. RMN 1 H (CDCI3, 300 MHz): δ 0,80 (t, 3JH,H = 8,2 Hz, 2H, SiCH2), 1 ,25 (t, 3JH,H = 7,0 Hz, 9H, CH3CH20), 2,25 (m, 2H, SiCH2CH2), 2,28 (s, 3H, pic-Me), 2,30 (s,
6H, Mes-o-Me), 2,34 (s, 3H, Mes-p-Me), 3,86 (c, 3 H,H = 7,0 Hz, 6H, CH3CH20), 4,62 (t, 3JH,h = 7,0 Hz, 2H, CH2lmz), 6,87 y 7,24 (2 x d, 3JH,H = 2,0 Hz, 2 x 1 H, Imz-H4 y H5), 6,97 (s, 2H, m-Mes), 6,98 (d, 3JH,H = 5,6 Hz, 2H, m-pic), 8,53 (d, 3JH,H = 5,6 Hz, 2H, o-pic). RMN 13C{1 H} (CDCI3, 75 MHz): 5 7,7 (SiCH2), 18,4 (CH3CH20), 21 ,0 (Mes-p-Me), 21 , 1 (pic-Me), 21 ,7 (Mes-o-Me), 23,3 (SiCH2CH2), 55,0 (CH2lmz), 58,6 (CH3CH20), 121 ,3 y 136,1 (Imz- C4 y C5), 125, 1 (m-pic), 129,4 (m-Mes), 135,0 (ipso- Mes), 139,0 (p-Mes), 148,4 (o-Mes), 149,1 (p-pic), 152,9 (o-pic). IR (KBr): v 3070-3160 (m, arC-H st), 1618 (m, arC=C st), 1531 (s, C=N st), 1400-1480 (m, arC=C st), 1076 (w, Si-O-C st), 956 (w, Si-O-C st), 806 (m, Si-C st), 692 crrf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 862,0312 [M + NH4]+, 845,0154 [M + H]+, 717,0939 [M - l]+. Compound 1 (Si) 2 was prepared as described for complex 1 (Si) 1 of Example 10, starting from the imidazolium salt 2 (Si) 2 described in Example 5 (0.57 g, 1, 2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.26 g, 8.4 mmol), in 12 ml_ of 4-picoline, at 100 ° C and for 16 h. Compound 1 (Si) 2 was obtained as an orange powdery solid (0.99 g, 98%). Anal. Cale, for C 27 H 41 0 3 N 3 1 2 SiPd (843.95): C, 38.43; H, 4.90; N, 4.98%. Found: C, 38.22; H, 4.78; N, 5.36%. 1 H NMR (CDCI 3 , 300 MHz): δ 0.80 (t, 3 J H, H = 8.2 Hz, 2H, SiCH 2 ), 1, 25 (t, 3 J H, H = 7.0 Hz, 9H, CH 3 CH 2 0), 2.25 (m, 2H, SiCH 2 CH 2 ), 2.28 (s, 3H, pic-Me), 2.30 (s, 6H, Month-o-Me), 2.34 (s, 3H, Month-p-Me), 3.86 (c, 3 H, H = 7.0 Hz, 6H, CH 3 CH 2 0), 4 , 62 (t, 3 JH , h = 7.0 Hz, 2H, CH 2 lmz), 6.87 and 7.24 (2 xd, 3 J H, H = 2.0 Hz, 2 x 1 H, Imz -H 4 and H 5 ), 6.97 (s, 2H, m-Month), 6.98 (d, 3 J H, H = 5.6 Hz, 2H, m-pic), 8.53 (d , 3 J H, H = 5.6 Hz, 2H, o-pic). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): 5 7.7 (SiCH 2 ), 18.4 (CH 3 CH 2 0), 21, 0 (Month-p-Me), 21, 1 ( pic-Me), 21, 7 (Month-o-Me), 23.3 (SiCH 2 CH 2 ), 55.0 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 121, 3 and 136.1 (Imz-C 4 and C 5 ), 125, 1 (m-pic), 129.4 (m-Month), 135.0 (ipso-Month), 139.0 (p-Month), 148 , 4 (o-Month), 149.1 (p-pic), 152.9 (o-pic). IR (KBr): v 3070-3160 (m, arC-H st), 1618 (m, arC = C st), 1531 (s, C = N st), 1400-1480 (m, arC = C st), 1076 (w, Si-OC st), 956 (w, Si-OC st), 806 (m, Si-C st), 692 crrf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 862.0312 [M + NH 4 ] + , 845.0154 [M + H] + , 717.0939 [M-l] + .
l(Si)2 l (Yes) 2
Ejemplo 12. Preparación del complejo de paladio l(Si)3. Example 12. Preparation of the palladium complex l (Si) 3.
El compuesto l(Si)3 se preparó de forma similar a la descrita para el complejo l(Si)1 del Ejemplo 10, partiendo de la sal de imidazolio 2(Si)3 descrita en el Ejemplo 6 (0,62 g, 1 ,2 mmol), cloruro de paladio (0,21 g, 1 ,2 mmol), carbonato de potasio (0,83 g, 6,0 mmol) y yoduro de sodio (1 ,28 g, 8,4 mmol), en 12 mL de 4-picolina, a 100 °C y durante 16 h. Se obtuvo el compuesto l(Si)3 como un sólido pulverulento de color naranja (0,99 g, 98%). Anal. Cale, para C3oH4703N3l2SiPd (843,95): C, 40,67; H, 5,35; N, 4,74%. Encontrado: C, 41 ,03; H, 5,75; N, 5,21 %. RMN 1 H (CDCI3, 300 MHz): δ 0,82 (d, 3JH,H = 7,9 Hz, 2H, SiCH2), 0,99 (d, 3JH,H = 6,9 Hz, 6H, CH(CH3)2), 1 ,24 (t, 3JH,H = 6,9 Hz, 9H, CH3CH20), 1 ,38 (d, 3JH,H = 6,9 Hz, 6H, CH(CH3)2), 2,23 (m, 2H, SiCH2CH2), 2,27 (s, 3H, pic-Me), 3, 10 (h, 3JH,H = 6,9 Hz, 6H, CH(CH3)2), 3,85 (c, 3JH,H = 6,9 Hz, 6H, CH3CH20), 4,68 (t, 3JH,H = 7,9 Hz, 2H, CH2lmz), 6,98 (2 x t, 3H, 3JH,H = 6,6 Hz, 3JH,H = 2,0 Hz, Imz-H4 y o-pic, solapados), 7, 13 (d, 3JH,H = 2,0 Hz, 1 H, Imz-H5), 7,28 (d, 3JH,H = 7,9 Hz, 2H, m-Ph), 7,46 (t, 3JH,H = 7,9 Hz, 1 H, p-Ph), 8,54 (d, 3JH,H = 6,6 Hz, 2H, o-pic). RMN 13C{1 H} (CDCI3, 75 MHz): δ 7,7 (SiCH2), 18,4 (CH3CH20), 21 ,0 (pic-Me), 23,2 (SiCH2CH2), 23,9 (CH(CH3)2), 26,5 (CH(CH3)2), 28,8 (CH(CH3)2), 55,4 (CH2lmz), 58,6 (CH3CH20), 120,3 y 130,3 (Imz-C4 y C5), 124,2 (m-Ph), 125, 1 (m-pic), 126,7 (p-Ph), 134,7 (/pso-Ph), 147,0 (o-Ph), 149, 1 (p-
pie), 152,8 (o-pic). ). IR (KBr): v 3030-3130 (m, arC-H st), 1619 (m, arC=C st), 1503 (s, C=N st), 1400-1460 (m, arC=C st), 1077 (w, Si-O-C st), 957 (w, Si-O-C st), 804 (m, Si-C st), 692 crrf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 904,0818 [M + NH4]+, 887,0560 [M + H]+. Compound 1 (Si) 3 was prepared in a manner similar to that described for complex 1 (Si) 1 of Example 10, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (0.62 g, 1 , 2 mmol), palladium chloride (0.21 g, 1.2 mmol), potassium carbonate (0.83 g, 6.0 mmol) and sodium iodide (1.28 g, 8.4 mmol), in 12 mL of 4-picoline, at 100 ° C and for 16 h. Compound 1 (Si) 3 was obtained as an orange powdery solid (0.99 g, 98%). Anal. Cale, for C 3 oH 47 0 3 N 3 l 2 SiPd (843.95): C, 40.67; H, 5.35; N, 4.74%. Found: C, 41, 03; H, 5.75; N, 5.21%. 1 H NMR (CDCI 3 , 300 MHz): δ 0.82 (d, 3 J H, H = 7.9 Hz, 2H, SiCH 2 ), 0.99 (d, 3 J H, H = 6.9 Hz, 6H, CH (CH 3 ) 2 ), 1, 24 (t, 3 J H, H = 6.9 Hz, 9H, CH 3 CH 2 0), 1, 38 (d, 3 J H, H = 6.9 Hz, 6H, CH (CH 3 ) 2 ), 2.23 (m, 2H, SiCH 2 CH 2 ), 2.27 (s, 3H, pic-Me), 3, 10 (h, 3 J H , H = 6.9 Hz, 6H, CH (CH 3 ) 2 ), 3.85 (c, 3 J H , H = 6.9 Hz, 6H, CH 3 CH 2 0), 4.68 (t , 3 J H , H = 7.9 Hz, 2H, CH 2 lmz), 6.98 (2 xt, 3H, 3 J H, H = 6.6 Hz, 3 J H, H = 2.0 Hz, Imz-H 4 and o-pic, overlapping), 7, 13 (d, 3 J H, H = 2.0 Hz, 1 H, Imz-H 5 ), 7.28 (d, 3 J H, H = 7.9 Hz, 2H, m-Ph), 7.46 (t, 3 J H, H = 7.9 Hz, 1 H, p-Ph), 8.54 (d, 3 J H, H = 6 , 6 Hz, 2H, o-pic). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 7.7 (SiCH 2 ), 18.4 (CH 3 CH 2 0), 21, 0 (pic-Me), 23.2 (SiCH 2 CH 2 ), 23.9 (CH (CH 3 ) 2 ), 26.5 (CH (CH 3 ) 2 ), 28.8 (CH (CH 3 ) 2 ), 55.4 (CH 2 lmz), 58 , 6 (CH 3 CH 2 0), 120.3 and 130.3 (Imz-C 4 and C 5 ), 124.2 (m-Ph), 125, 1 (m-pic), 126.7 (p -Ph), 134.7 (/ pso-Ph), 147.0 (o-Ph), 149, 1 (p- foot), 152.8 (o-pic). ). IR (KBr): v 3030-3130 (m, arC-H st), 1619 (m, arC = C st), 1503 (s, C = N st), 1400-1460 (m, arC = C st), 1077 (w, Si-OC st), 957 (w, Si-OC st), 804 (m, Si-C st), 692 crrf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 904.0818 [M + NH 4 ] + , 887.0560 [M + H] + .
l(Si)3 l (Yes) 3
Ejemplo 13. Preparación del complejo de plata 3(Si)1. En una ampolla de 50 mL se pesó la sal de imidazolio 2(Si)1 descrita en el Ejemplo 4 (1 ,28 g, 3,5 mmol) y el óxido de plata (0,40 g, 1 ,7 mmol), y se hizo vacío durante 10 min. Se suspendió el sólido en 10 mL de diclorometano bajo argón y se dejó agitando la mezcla a temperatura ambiente durante 16 h en ausencia de luz. Tras filtrar para eliminar el exceso de óxido de plata, se evaporó la disolución amarilla resultante y el residuo se lavó con hexano (2 x 15 mL), obteniéndose el producto 3(Si)1 como un sólido aceitoso de color amarillo (1 ,48 g, 95%), cuya estructura en disolución se corresponde con una formulación [Ag(NHC)2][AgBr2] que da lugar a los rotámeros syn y anti (70:30) en equilibrio. Anal. Cale, para C26H52N406Si2Ag2Br2 (948,43): C, 32,93; H, 5,53; N, 5,91 %; Encontrado: C, 32,93; H, 5,28; N, 5,93%. RMN 1 H (CDCI3, 300 MHz): Isómero anti: 5 0,56 (t, 3JH,H = 7,7 Hz, 4H, SiCH2), 1 , 19 (t, 3 H,H = 6,9 Hz, 18H, CH3CH20), 1 ,88 (m, 4H, SiCH2CH2), 3,76 (s, 6H, Imz-Me), 3,78 (c, 3JH,H = 6,9 Hz, 12H, CH3CH20), 4,08 (t, 3JH,H = 7,7 Hz, 4H, CH2lmz), 6,91 y 6,94 (d, 3JH,H = 1 ,5 Hz, 2H, lmz-H4 y H5). Isómero syn: 5 0,55 (t, 3JH,H = 7,7 Hz, 4H, SiCH2), 1 , 18 (t, 3JH,H = 6,9 Hz, 18H, CH3CH20), 1 ,88 (m, 4H, SiCH2CH2), 3,78 (c, 3JH,H = 6,9 Hz, 12H, CH3CH20), 3,79 (s, 6H, Imz-Me), 4,06 (t, 3JH,H = 7,7 Hz, 4H, CH2lmz), 6,93 y 6,98 (d, 3JH,H = 1 ,5 Hz, 2H, lmz-H4 y H5). RMN 13C{1 H} (CDCI3, 75 MHz): Isómero anti: 5 8,7 (SiCH2), 18,2 (CH3CH20), 25,6 (SiCH2CH2), 38,9 (Imz-Me), 54, 1 (CH2lmz), 58,3 (CH3CH20), 121 ,2 y 122,1 (Imz-C4 y C5), 181 ,7 (Imz-C2). Isómero syn: 5 7,3 (SiCH2), 18,2 (CH3CH20), 25,2 (SiCH2CH2), 38,7 (Imz-Me), 53,9 (CH2lmz), 58,5 (CH3CH20), 121 ,0 y 122,0 (Imz-C4 y C5), 181 ,2 (Imz-C2). Coeficientes de difusión DOSY- NMR (CDCI3, 25 °C) en torno a 6,0- 10"10 m2s 1 para los dos rotámeros. MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 681 ,2542 [Ag(NHC)2]+, 287, 1814 [NHC + H]+.
Example 13. Preparation of the silver complex 3 (Si) 1. The imidazolium 2 (Si) 1 salt described in Example 4 (1.28 g, 3.5 mmol) and the silver oxide (0.40 g, 1.7 mmol) were weighed in a 50 mL ampoule. and it was empty for 10 min. The solid was suspended in 10 mL of dichloromethane under argon and the mixture was allowed to stir at room temperature for 16 h in the absence of light. After filtering to remove excess silver oxide, the resulting yellow solution was evaporated and the residue was washed with hexane (2 x 15 mL), yielding product 3 (Si) 1 as a yellow oily solid (1, 48 g, 95%), whose structure in solution corresponds to a formulation [Ag (NHC) 2 ] [AgBr 2 ] that gives the syn and anti rotamers (70:30) in equilibrium. Anal. Cale, for C 26 H 52 N 4 0 6 Si 2 Ag 2 Br 2 (948.43): C, 32.93; H, 5.53; N, 5.91%; Found: C, 32.93; H, 5.28; N, 5.93%. 1 H NMR (CDCI 3 , 300 MHz): Anti isomer: 5.56 (t, 3 J H, H = 7.7 Hz, 4H, SiCH 2 ), 1, 19 (t, 3 H, H = 6 , 9 Hz, 18H, CH 3 CH 2 0), 1, 88 (m, 4H, SiCH 2 CH 2 ), 3.76 (s, 6H, Imz-Me), 3.78 (c, 3 J H, H = 6.9 Hz, 12H, CH 3 CH 2 0), 4.08 (t, 3 J H, H = 7.7 Hz, 4H, CH 2 lmz), 6.91 and 6.94 (d, 3 J H, H = 1.5 Hz, 2H, lmz-H 4 and H 5 ). Syn isomer: 5 0.55 (t, 3 J H, H = 7.7 Hz, 4H, SiCH 2 ), 1, 18 (t, 3 J H, H = 6.9 Hz, 18H, CH 3 CH 2 0), 1, 88 (m, 4H, SiCH 2 CH 2 ), 3.78 (c, 3 J H, H = 6.9 Hz, 12H, CH 3 CH 2 0), 3.79 (s, 6H , Imz-Me), 4.06 (t, 3 J H, H = 7.7 Hz, 4H, CH 2 lmz), 6.93 and 6.98 (d, 3 J H, H = 1.5 Hz , 2H, lmz-H 4 and H 5 ). NMR 13 C {1 H} (CDCI 3, 75 MHz): Isomer anti: 5 8.7 (SiCH 2), 18.2 (CH 3 CH 2 0), 25.6 (SiCH 2 CH 2) 38, 9 (Imz-Me), 54, 1 (CH 2 lmz), 58.3 (CH 3 CH 2 0), 121, 2 and 122.1 (Imz-C 4 and C 5 ), 181, 7 (Imz- C 2 ). Syn isomer: 5 7.3 (SiCH 2 ), 18.2 (CH 3 CH 2 0), 25.2 (SiCH 2 CH 2 ), 38.7 (Imz-Me), 53.9 (CH 2 lmz) , 58.5 (CH 3 CH 2 0), 121, 0 and 122.0 (Imz-C 4 and C 5 ), 181, 2 (Imz-C 2 ). Diffusion coefficients DOSY-NMR (CDCI 3 , 25 ° C) around 6.0-10 "10 m 2 s 1 for the two rotamers. MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM) : m / z 681, 2542 [Ag (NHC) 2 ] + , 287, 1814 [NHC + H] + .
3(Si)1 3 (Yes) 1
Ejemplo 14. Preparación del complejo de plata 3(Si)2. Example 14. Preparation of silver complex 3 (Si) 2.
El compuesto 3(Si)2 se preparó de como se describe para el complejo 3(Si)1 del Ejemplo 13, partiendo de la sal de imidazolio 2(Si)2 descrita en el Ejemplo 5 (2,69 g, 5,7 mmol) y óxido de plata (0,66 g, 2,8 mmol). El complejo 3(Si)2 se obtuvo como un sólido aceitoso de color amarillo (3,07 g, 98%), cuya estructura en disolución se corresponde con una formulación [Ag(NHC)2][AgBr2] que da lugar a los rotámeros syn y anti (70:30) en equilibrio. Anal. Cale, para C42H68N4O6Si2Ag2Br2 0,7CH2CI2 (1207,69): C, 42, 17; H, 5,75; N, 4,81 %; Encontrado: C, 41 ,83; H, 5, 16; N, 5,27%. RMN 1 H (CDCI3, 300 MHz): Isómeros anti y syn: δ 0,57 (m, 8H, SiCH2), 1 ,21 (t, 3 H,H = 7,0 Hz, 36H, CH3CH20), 1 ,79 (m, 8H, SiCH2CH2), 1 ,93 (s, 24H, Mes- o- Me), 2,29 (s, 12H, Mes-p-Me), 3,79 (c, 3 H,H = 7,0 Hz, 24H, CH3CH20), 4, 18 (m, 8H, CH2lmz), 6,89 y 7, 18 (2 x d, 3JH,H = 1 ,5 Hz,2 χ 4H, Imz-H4 y H5), 6,91 (s, 8H, m-Mes). RMN 13C{1 H} (CDCI3, 75 MHz): Isómero anti: 5 8,5 (SiCH2), 17,7 (CH3CH20), 21 ,0 (Mes-p-Me), 25,7 (SiCH2CH2), 29, 1 (Mes-o-Me), 53,7 (CH2lmz), 58, 1 (CH3CH20), 121 ,6 y 123,9 (Imz-C4 y C5), 129,4 (m-Mes), 134,6 (o-Mes), 135,3 (/pso-Mes), 139,1 (p-Mes). Isómero syn: δ 7,3 (SiCH2), 18,3 (CH3CH20), 21 ,0 (Mes-p-Me), 25,3 (SiCH2CH2), 29, 1 (Mes-o-Me), 54,0 (CH2lmz), 58,5 (CH3CH20), 120,9 y 122,5 (Imz-C4 y C5), 129, 1 (m-Mes), 134,7 (o-Mes), 135,6 (/pso-Mes), 139,3 (p-Mes). Coeficientes de difusión DOSY-NMR (CDCI3, 25 °C) en torno a 5,8- 10"10 mV para los dos rotámeros. MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 889,3779 [Ag(NHC)2]+. Compound 3 (Si) 2 was prepared as described for complex 3 (Si) 1 of Example 13, starting from the imidazolium 2 (Si) 2 salt described in Example 5 (2.69 g, 5.7 mmol) and silver oxide (0.66 g, 2.8 mmol). Complex 3 (Si) 2 was obtained as a yellow oily solid (3.07 g, 98%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2 ] [AgBr 2 ] that results in rotámeros syn and anti (70:30) in balance. Anal. Cale, for C 42 H 68 N 4 O 6 Si 2 Ag 2 Br 2 0.7CH 2 CI 2 (1207.69): C, 42, 17; H, 5.75; N, 4.81%; Found: C, 41, 83; H, 5, 16; N, 5.27%. 1 H NMR (CDCI 3 , 300 MHz): Anti and syn isomers: δ 0.57 (m, 8H, SiCH 2 ), 1, 21 (t, 3 H, H = 7.0 Hz, 36H, CH 3 CH 2 0), 1, 79 (m, 8H, SiCH 2 CH 2 ), 1, 93 (s, 24H, Month-o-Me), 2.29 (s, 12H, Month-p-Me), 3, 79 (c, 3 H, H = 7.0 Hz, 24H, CH 3 CH 2 0), 4, 18 (m, 8H, CH 2 lmz), 6.89 and 7, 18 (2 xd, 3 J H , H = 1.5 Hz, 2 χ 4H, Imz-H 4 and H 5 ), 6.91 (s, 8H, m-Month). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): Anti isomer: 5 8.5 (SiCH 2 ), 17.7 (CH 3 CH 2 0), 21, 0 (Month-p-Me), 25 , 7 (SiCH 2 CH 2 ), 29, 1 (Month-o-Me), 53.7 (CH 2 lmz), 58, 1 (CH 3 CH 2 0), 121, 6 and 123.9 (Imz- C 4 and C 5 ), 129.4 (m-Month), 134.6 (o-Month), 135.3 (/ pso-Month), 139.1 (p-Month). Syn isomer: δ 7.3 (SiCH 2 ), 18.3 (CH 3 CH 2 0), 21, 0 (Month-p-Me), 25.3 (SiCH 2 CH 2 ), 29, 1 (Month- o-Me), 54.0 (CH 2 lmz), 58.5 (CH 3 CH 2 0), 120.9 and 122.5 (Imz-C 4 and C 5 ), 129, 1 (m-Month) , 134.7 (o-Month), 135.6 (/ pso-Month), 139.3 (p-Month). Diffusion coefficients DOSY-NMR (CDCI 3 , 25 ° C) around 5.8-10 "10 mV for the two rotamers. MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 889.3779 [Ag (NHC) 2 ] + .
(EtO)3Si ^^ N^N. Mes (EtO) 3 Yes ^^ N ^ N. Month
AgBr AgBr
3(s¡)2 3 ( yes ) 2
Ejemplo 15. Preparación del complejo de plata 3(Si)3. Example 15. Preparation of the silver complex 3 (Si) 3.
El compuesto 3(Si)3 se preparó de como se describe para el complejo 3(Si)1 del Ejemplo 13, partiendo de la sal de imidazolio 2(Si)3 descrita en el Ejemplo 6 (2,50 g, 5,2 mmol) y
óxido de plata (0,60 g, 2,6 mmol). El complejo 3(Si)3 se obtuvo como un sólido aceitoso de color amarillo (3, 14 g, 98%), cuya estructura en disolución se corresponde con una formulación [Ag(NHC)2][AgBr2] que da lugar a los rotámeros syn y anti (70:30) en equilibrio. Anal. Cale, para C48H8oN406Si2Ag2Br2 (1240,89): C, 46,46; H, 6,50; N, 4,51 %; Encontrado: C, 46,84; H, 6,88; N, 5,01 %. RMN 1 H (CDCI3, 300 MHz): Isómeros anti y syn: δ 0,67 (m, 8H, SiCH2), 1 , 15 (d, 3 H,H = 6,6 Hz, 24H, CH(CH3)2), 1 ,20 (d, 3 H,H = 6,6 Hz, 24H, CH(CH3)2), 1 ,21 (t, 3JH,H = 7,0 Hz, 36H, CH3CH20), 2,03 (m, 8H, SiCH2CH2), 2,36 (sep., 3JH,H = 6,6 Hz, 8H, CH(CH3)2), 3,85 (c, 3JH,H = 7,0 Hz, 24H, CH3CH20), 4,33 (m, 8H, CH2lmz), 7,00 y 7,20 (2 x d, 3JH,H = 1 ,7 Hz,2 χ 4H, Imz-H4 y H5), 7,22 (d, 3JH,H = 7,7 Hz, 8H, m-Ph), 7,47 (t, 3JH,H = 7,7 Hz, 4H, p-Ph). RMN 13C{1 H} (CDCI3, 75 MHz): Isómero anti: 5 7,5 (SiCH2), 18,3 (CH3CH20), 24,3 (CH(CH3)2), 25,4 (SiCH2CH2), 28, 1 (CH(CH3)2), 54, 1 (CH2lmz), 58,6 (CH3CH20), 121 ,5 y 123,7 (Imz-C4 y C5), 124,2 (p-Ph), 129,7 (m-Ph), 145,6 (o-Ph), 145,9 (/pso-Ph). Isómero syn: δ 7,3 (SiCH2), 18,3 (CH3CH20), 24,5 (CH(CH3)2), 25,2 (SiCH2CH2), 28,3 (CH(CH3)2), 53,7 (CH2lmz), 58,5 (CH3CH20), 121 ,5 y 123,7 (Imz-C4 y C5), 125,7 (p-Ph), 130,5 (m-Ph), 145,6 (o-Ph), 145,9 (/pso-Ph). Coeficientes de difusión DOSY-NMR (CDCI3, 25 °C) en torno a 5,7- 10"10 mV para los dos rotámeros. MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 973,4667 [Ag(NHC)2]+. Compound 3 (Si) 3 was prepared as described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (Si) 3 described in Example 6 (2.50 g, 5.2 mmol) and silver oxide (0.60 g, 2.6 mmol). Complex 3 (Si) 3 was obtained as a yellow oily solid (3.14 g, 98%), whose dissolving structure corresponds to a formulation [Ag (NHC) 2 ] [AgBr 2 ] which results in rotámeros syn and anti (70:30) in balance. Anal. Cale, for C 48 H 8 oN 4 0 6 Si 2 Ag 2 Br 2 (1240.89): C, 46.46; H, 6.50; N, 4.51%; Found: C, 46.84; H, 6.88; N, 5.01%. 1 H NMR (CDCI 3 , 300 MHz): Anti and syn isomers: δ 0.67 (m, 8H, SiCH 2 ), 1, 15 (d, 3 H, H = 6.6 Hz, 24H, CH (CH 3 ) 2 ), 1, 20 (d, 3 H, H = 6.6 Hz, 24H, CH (CH 3 ) 2 ), 1, 21 (t, 3 J H, H = 7.0 Hz, 36H, CH 3 CH 2 0), 2.03 (m, 8H, SiCH 2 CH 2 ), 2.36 (Sep., 3 J H, H = 6.6 Hz, 8H, CH (CH 3 ) 2 ), 3 , 85 (c, 3 J H, H = 7.0 Hz, 24H, CH 3 CH 2 0), 4.33 (m, 8H, CH 2 lmz), 7.00 and 7.20 (2 xd, 3 J H, H = 1, 7 Hz, 2 χ 4H, Imz-H 4 and H 5 ), 7.22 (d, 3 J H, H = 7.7 Hz, 8H, m-Ph), 7.47 (t, 3 J H, H = 7.7 Hz, 4H, p-Ph). NMR 13 C {1 H} (CDCI 3, 75 MHz): Isomer anti: 5 7.5 (SiCH 2), 18.3 (CH 3 CH 2 0), 24.3 (CH (CH 3) 2), 25.4 (SiCH 2 CH 2 ), 28, 1 (CH (CH 3 ) 2 ), 54, 1 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 121, 5 and 123.7 ( Imz-C 4 and C 5 ), 124.2 (p-Ph), 129.7 (m-Ph), 145.6 (o-Ph), 145.9 (/ pso-Ph). Syn isomer: δ 7.3 (SiCH 2 ), 18.3 (CH 3 CH 2 0), 24.5 (CH (CH 3 ) 2 ), 25.2 (SiCH 2 CH 2 ), 28.3 (CH (CH 3 ) 2 ), 53.7 (CH 2 lmz), 58.5 (CH 3 CH 2 0), 121, 5 and 123.7 (Imz-C 4 and C 5 ), 125.7 (p- Ph), 130.5 (m-Ph), 145.6 (o-Ph), 145.9 (/ pso-Ph). Diffusion coefficients DOSY-NMR (CDCI 3 , 25 ° C) around 5.7-10 "10 mV for the two rotamers. MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 973.4667 [Ag (NHC) 2 ] + .
3(Si)3 3 (Yes) 3
Ejemplo 16. Preparación del complejo de plata 3(A)1. Example 16. Preparation of the silver complex 3 (A) 1.
El compuesto 3(A)1 se preparó de forma similar a la descrita para el complejo 3(Si)1 del Ejemplo 13, partiendo de la sal de imidazolio 2(A)1 descrita en el Ejemplo 7 (0,80 g, 3,7 mmol) y óxido de plata (0,43 g, 1 ,9 mmol). El complejo 3(A)1 se obtuvo como un sólido aceitoso de color amarillo (1 ,03 g, 88%). Anal. Cale, para CeHu NsAgBr O. I CeHn (321 ,56): C, 24,65; H, 3,89; N, 13,07%; Encontrado: C, 24,95; H, 4,09; N, 13,25%. RMN 1 H (CDCI3, 300 MHz): δ 3,09 (t, 3JH,H = 5,5 Hz, 2H, NH2CH2), 3,83 (s, 3H, Imz-Me), 4, 14 (t, 3JH,H = 5,5 Hz, 2H, CH2lmz), 6,96 y 7,05 (2 x d, 3JH,H = 1 ,8 HZ, 2 χ 1 H, Imz-H4 y H5). RMN 13C{1 H} (CDCI3, 75 MHz): 5 38,8 (Imz-Me), 42,9 (NH2CH2), 54,7 (CH2lmz), 121 ,6 y 122, 1 (Imz-C4 y C5), 180,8 (Imz-C2). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 287, 1763 [M - Br + 3H20]+.
f=\ Compound 3 (A) 1 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 1 described in Example 7 (0.80 g, 3 , 7 mmol) and silver oxide (0.43 g, 1.9 mmol). Complex 3 (A) 1 was obtained as a yellow oily solid (1.03 g, 88%). Anal. Cale, for CeHu NsAgBr O. I CeHn (321, 56): C, 24.65; H, 3.89; N, 13.07%; Found: C, 24.95; H, 4.09; N, 13.25%. 1 H NMR (CDCI 3 , 300 MHz): δ 3.09 (t, 3 J H, H = 5.5 Hz, 2H, NH 2 CH 2 ), 3.83 (s, 3H, Imz-Me), 4, 14 (t, 3 J H, H = 5.5 Hz, 2H, CH 2 lmz), 6.96 and 7.05 (2 xd, 3 J H, H = 1, 8 HZ, 2 χ 1 H , Imz-H 4 and H 5 ). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): 5 38.8 (Imz-Me), 42.9 (NH 2 CH 2 ), 54.7 (CH 2 lmz), 121, 6 and 122, 1 (Imz-C 4 and C 5 ), 180.8 (Imz-C 2 ). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 287, 1763 [M-Br + 3H 2 0] + . f = \
Η,Ν Η, Ν
AgBr AgBr
3(A)1 3 (A) 1
Ejemplo 17. Preparación del complejo de plata 3(A)2. Example 17. Preparation of silver complex 3 (A) 2.
El compuesto 3(A)2 se preparó de forma similar a la descrita para el complejo 3(Si)1 del Ejemplo 13, partiendo de la sal de imidazolio 2(A)2 descrita en el Ejemplo 8 (3,20 g, 10,0 mmol) y óxido de plata (1 ,18 g, 5,1 mmol). El complejo 3(A)2 se obtuvo como un sólido aceitoso de color amarillo (3,60 g, 86%). Anal. Cale, para Ci4H19N3AgBr 0, 15(C6H14) (430,02): C, 41 ,61 ; H, 4,95; N, 9,77%; Encontrado: C, 42,07; H, 4,91 ; N, 10,29%. RMN 1 H (CDCI3, 300 MHz): δ 1 ,93 (s, 6H, Mes- o- Me), 2,31 (s, 3H, Mes-p-Me), 3, 15 (t, 3 H,H = 5,6 Hz, 2H, N H2CH2), 4,25 (t, 3JH,H = 5,6 Hz, 2H, CH2lmz), 6,91 y 7,28 (2 x d, 3JH,H = 1 ,7 Hz, 2 x 1 H, Imz-H4 y H5), 6,92 (s, 2H, m-Mes). RMN 13C{1 H} (CDCI3, 75 MHz): δ 17,7 (Mes-p- Me), 21 , 1 (Mes-o-Me), 43, 1 (CH2lmz), 55,0 (NH2CH2), 121 ,4 y 122,6 (Imz-C4 y C5), 129,4 (m-Mes), 135,3 (/pso-Mes), 134,6 (o-Mes), 139,6 (p-Mes), 180,2 (Imz-C2). MS (ESlVTOF CH2CI2/MeOH/NH4HCOO 5 mM): m/z 230.1656 [M - AgBr + H]+. Compound 3 (A) 2 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 2 described in Example 8 (3.20 g, 10 , 0 mmol) and silver oxide (1.18 g, 5.1 mmol). Complex 3 (A) 2 was obtained as a yellow oily solid (3.60 g, 86%). Anal. Cale, for Ci 4 H 19 N 3 AgBr 0.15 (C 6 H 14 ) (430.02): C, 41, 61; H, 4.95; N, 9.77%; Found: C, 42.07; H, 4.91; N, 10.29%. 1 H NMR (CDCI 3 , 300 MHz): δ 1, 93 (s, 6H, Mes-o-Me), 2.31 (s, 3H, Month-p-Me), 3, 15 (t, 3 H , H = 5.6 Hz, 2H, N H2CH2), 4.25 (t, 3 J H, H = 5.6 Hz, 2H, CH 2 lmz), 6.91 and 7.28 (2 xd, 3 J H, H = 1, 7 Hz, 2 x 1 H, Imz-H 4 and H 5 ), 6.92 (s, 2H, m-Month). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): δ 17.7 (Month-p-Me), 21, 1 (Month-o-Me), 43, 1 (CH 2 lmz), 55.0 (NH 2 CH 2 ), 121, 4 and 122.6 (Imz-C 4 and C 5 ), 129.4 (m-Month), 135.3 (/ pso-Month), 134.6 (o-Month ), 139.6 (p-Month), 180.2 (Imz-C 2 ). MS (ESlVTOF CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 230.1656 [M - AgBr + H] + .
3(A)2 Ejemplo 18. Preparación del complejo de plata 3(A)3. 3 (A) 2 Example 18. Preparation of the silver complex 3 (A) 3.
El compuesto 3(A)3 se preparó de forma similar a la descrita para el complejo 3(Si)1 del Ejemplo 13, partiendo de la sal de imidazolio 2(A)3 descrita en el Ejemplo 9 (3,60 g, 10,3 mmol) y óxido de plata (1 ,18 g, 5,1 mmol). El complejo 3(A)3 se obtuvo como un sólido aceitoso de color amarillo (4,30 g, 90%). Anal. Cale, para Ci7H25N3AgBr 0,25(C6H14) (480,72): C, 46,22; H, 5,98; N, 8,74%; Encontrado: C, 46,75; H, 5,72; N, 8,53%. RMN 1 H (CDCI3, 300 MHz): 5 1 , 1 1 (d, 3JH,H = 6,9 Hz, 12H, CH(CH3)2), 1 , 18 (d, 3JH,H = 6,9 Hz, 12H, CH(CH3)2), 2,32 (sep., 3 H,H = 6,9 Hz, 2H, (CH3)2CH), 3, 17 (t, 3 H,H = 5,8 Hz, 2H, NH2CH2), 4,26 (t, 3JH,H = 5,8 Hz, 2H, CH2lmz), 6,98 y 7,31 (2 x d, 3JH,H = 1 ,5 HZ, 2 χ 1 H, Imz-H4 y H5), 7,23 (d, 3JH,H = 7,7 Hz, 2H, m-Ph), 7,45 (t, 3JH,H = 7,7 Hz, 1 H, p-Ph). RMN 13C{1 H}
(CDCI3, 75 MHz): δ 24,3 (CH(CH3)2), 24,6 (CH(CH3)2), 28,3 (CH(CH3)2), 43,2 (NH2CH2), 55,0 (CH2lmz), 121 ,2 y 123,9 (Imz-C4 y C5), 124,3 (m-Ph), 130,5 (/pso-Ph), 134,6 (o-Ph), 145,6 (p-Ph), 182,8 (Imz-C2). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 272,2139 [M - AgBr + H]+. f=\Compound 3 (A) 3 was prepared similarly to that described for complex 3 (Si) 1 of Example 13, starting from the imidazolium salt 2 (A) 3 described in Example 9 (3.60 g, 10 , 3 mmol) and silver oxide (1.18 g, 5.1 mmol). Complex 3 (A) 3 was obtained as a yellow oily solid (4.30 g, 90%). Anal. Cale, for Ci 7 H 25 N 3 AgBr 0.25 (C 6 H 14 ) (480.72): C, 46.22; H, 5.98; N, 8.74%; Found: C, 46.75; H, 5.72; N, 8.53%. 1 H NMR (CDCI 3 , 300 MHz): 5 1, 1 1 (d, 3 J H, H = 6.9 Hz, 12 H, CH (CH 3 ) 2 ), 1, 18 (d, 3 J H, H = 6.9 Hz, 12H, CH (CH 3 ) 2 ), 2.32 (Sep., 3 H, H = 6.9 Hz, 2H, (CH 3 ) 2 CH), 3, 17 (t, 3 H, H = 5.8 Hz, 2H, NH 2 CH 2 ), 4.26 (t, 3 J H, H = 5.8 Hz, 2H, CH 2 lmz), 6.98 and 7.31 ( 2 xd, 3 J H, H = 1, 5 HZ, 2 χ 1 H, Imz-H 4 and H 5 ), 7.23 (d, 3 J H, H = 7.7 Hz, 2H, m-Ph ), 7.45 (t, 3 J H, H = 7.7 Hz, 1 H, p-Ph). 13 C NMR { 1 H} (CDCI3, 75 MHz): δ 24.3 (CH (CH 3 ) 2 ), 24.6 (CH (CH 3 ) 2 ), 28.3 (CH (CH 3 ) 2 ), 43.2 (NH 2 CH 2 ), 55.0 (CH 2 lmz), 121, 2 and 123.9 (Imz-C 4 and C 5 ), 124.3 (m-Ph), 130.5 (/ pso-Ph), 134 , 6 (o-Ph), 145.6 (p-Ph), 182.8 (Imz-C 2 ). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 272.2139 [M-AgBr + H] + . f = \
\ N . \ N.
H2N y "'Pr2Ph H 2 N and " 'Pr 2 Ph
AgBr AgBr
3(A)3 3 (A) 3
Ejemplo 19. Preparación del complejo de paladio ll(Si)1. En una ampolla de 50 ml_ se pesaron el carbeno de plata 3(Si)1 descrito en el Ejemplo 13 (0,39 g, 0,87 mmol) y PdBr2(COD) (0,16 g, 0,43 mmol; COD = 1 ,5-ciclooctadieno). Después de someter los sólidos a vacío durante 5 min, se disolvió el sólido bajo argón en 10 mL de diclorometano y la disolución naranja resultante se dejó agitando a temperatura ambiente durante 1 h. Se filtró la mezcla para separar el haluro de plata que se forma como producto secundario, se evaporó la disolución amarilla resultante y se lavó con hexano (2 x 15 mL), obteniéndose el producto ll(Si)1 como un sólido pulverulento de color amarillo (0,65 g, 89%), cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (50:50) en equilibrio. Anal. Cale, para C26H52N406Si2PdBr2 (839, 11): C, 37,22; H 6,25; N 6,68%; Encontrado: C, 36,97; H, 6,07; N, 6,79%. RMN 1 H (CDCI3, 300 MHz): Isómero anti: 5 0,72 (m, 4H, SiCH2), 1 ,20 (t, 3 H,H = 6,9 Hz, 18H, CH3CH20), 2,20 (m, 4H, SiCH2CH2), 3,81 (c, 3 H,H = 6,9 Hz, 12H, CH3CH20), 4,06 (s, 6H, Imz-Me), 4,44 (m, 4H, CH2lmz), 6,79 y 6,88 (2 x d, 3JH,H = 1 ,7 HZ, 2 χ 2H, Imz-H4 y H5). Isómero syn: 5 0,72 (m, 4H, SiCH2), 1 ,20 (t, 3JH,H = 6,9 Hz, 18H, CH3CH20), 2,20 (m, 4H, SiCH2CH2), 3,81 (c, 3JH,H = 6,9 Hz, 12H, CH3CH20), 4,03 (s, 6H, Imz-Me), 4,44 (m, 4H, CH2lmz), 6,79 y 6,86 (2 x d, 3JH,H = 1 ,7 HZ, 2 χ 2H, Imz-H4 y H5). RMN 13C{1 H} (CDCI3, 75 MHz): Isómero anti: 5 7,7 (SiCH2), 18,3 (CH3CH20), 24,4 (SiCH2CH2), 37,9 (Imz-Me), 53, 1 (CH2lmz), 58,6 (CH3CH20), 121 ,1 y 121 ,8 (Imz-C4 y C5), 169,2 (Imz- C4). Isómero syn: 5 7,5 (SiCH2), 18,3 (CH3CH20), 24,3 (SiCH2CH2), 37,9 (Imz-Me), 52,8 (CH2lmz), 58,5 (CH3CH20), 121 ,0 y 121 ,7 (Imz-C4 y C5), 169,2 (Imz-C2). IR (KBr): v 3080- 3150 (m, arC-H st), 1525 (s, C=N st), 1380-1480 (m, arC=C st), 1080 (w, Si-O-C st), 960 (w, Si-O-C st), 720-790 (m, Si-C st), 690 errf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 856, 1 157 [M + NH4]+, 759, 1635 [M - Br]+.
(EtO)3Si Example 19. Preparation of the palladium complex ll (Si) 1. In a 50 ml_ ampoule, the silver carbine 3 (Si) 1 described in Example 13 (0.39 g, 0.87 mmol) and PdBr 2 (COD) (0.16 g, 0.43 mmol; COD = 1,5-cyclooctadiene). After the solids were subjected to vacuum for 5 min, the solid was dissolved under argon in 10 mL of dichloromethane and the resulting orange solution was allowed to stir at room temperature for 1 h. The mixture was filtered to separate the silver halide that forms as a secondary product, the resulting yellow solution was evaporated and washed with hexane (2 x 15 mL), yielding product ll (Si) 1 as a yellow powdery solid. (0.65 g, 89%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti (50:50) rotamers in equilibrium. Anal. Cale, for C 2 6H 52 N 4 0 6 Si 2 PdBr 2 (839, 11): C, 37.22; H 6.25; N 6.68%; Found: C, 36.97; H, 6.07; N, 6.79%. 1 H NMR (CDCI 3 , 300 MHz): Anti isomer: 5.72 (m, 4H, SiCH 2 ), 1, 20 (t, 3 H, H = 6.9 Hz, 18H, CH 3 CH 2 0 ), 2.20 (m, 4H, SiCH 2 CH 2 ), 3.81 (c, 3 H, H = 6.9 Hz, 12H, CH 3 CH 2 0), 4.06 (s, 6H, Imz -Me), 4.44 (m, 4H, CH 2 lmz), 6.79 and 6.88 (2 xd, 3 J H, H = 1, 7 HZ, 2 χ 2H, Imz-H 4 and H 5 ). Syn isomer: 5.72 (m, 4H, SiCH 2 ), 1, 20 (t, 3 J H, H = 6.9 Hz, 18H, CH 3 CH 2 0), 2.20 (m, 4H, SiCH 2 CH 2 ), 3.81 (c, 3 J H, H = 6.9 Hz, 12H, CH 3 CH 2 0), 4.03 (s, 6H, Imz-Me), 4.44 (m , 4H, CH 2 lmz), 6.79 and 6.86 (2 xd, 3 J H, H = 1, 7 HZ, 2 χ 2H, Imz-H 4 and H 5 ). NMR 13 C {1 H} (CDCI 3, 75 MHz): Isomer anti: 5 7.7 (SiCH 2), 18.3 (CH 3 CH 2 0), 24.4 (SiCH 2 CH 2) 37, 9 (Imz-Me), 53, 1 (CH 2 lmz), 58.6 (CH 3 CH 2 0), 121, 1 and 121, 8 (Imz-C 4 and C 5 ), 169.2 (Imz- C 4 ). Syn isomer: 5 7.5 (SiCH 2 ), 18.3 (CH 3 CH 2 0), 24.3 (SiCH 2 CH 2 ), 37.9 (Imz-Me), 52.8 (CH 2 lmz) , 58.5 (CH 3 CH 2 0), 121, 0 and 121, 7 (Imz-C 4 and C 5 ), 169.2 (Imz-C 2 ). IR (KBr): v 3080-3150 (m, arC-H st), 1525 (s, C = N st), 1380-1480 (m, arC = C st), 1080 (w, Si-OC st), 960 (w, Si-OC st), 720-790 (m, Si-C st), 690 errf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 856, 1 157 [M + NH 4 ] + , 759, 1635 [M-Br] + . (EtO) 3 Yes
¾Si(OEt)3 ¾ Yes (OEt) 3
ll(Si)1 ll (Yes) 1
Ejemplo 20. Preparación del complejo de paladio ll(Si)2. El compuesto ll(Si)2 se preparó del mismo modo que el compuesto ll(Si)1 del Ejemplo 19, partiendo del carbeno de plata 3(Si)2 descrito en el Ejemplo 14 (0,45 g, 0,81 mmol) y de PdBr2(COD) (0, 15 g, 0,41 mmol). El complejo ll(Si)2 se obtuvo como un sólido pulverulento de color amarillo (0,83 g, 97%), cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (56:44) en equilibrio. Anal. Cale. C42H68N406Si2PdBr2 (1047,41): C, 48, 16; H, 6,54; N, 5,35%; Encontrado: C, 48,41 ; H, 6,44; N, 5,41 %. RMN 1 H (CDCI3, 300 MHz): Isómero anti: 5 0,47 (m, 4H, SiCH2), 1 ,20 (m, 18H, CH3CH20), 1 ,89 (m, 4H, SiCH2CH2), 2,22 (s, 12H, Mes-o-Me), 2,33 (s, 6H, Mes-p-Me), 3,83 (m, 12H, CH3CH20), 4, 17 (m, 4H, CH2lmz), 6,70 y 6,98 (2 x d, 3 H,H = 1 ,5 Hz, 2 x 2H, Imz-H4 y H5), 6,94 (s, 4H, m-Mes). Isómero syn: δ 0,73 (m, 4H, SiCH2), 1 ,23 (m, 18H, CH3CH2O), 1 ,89 (m, 4H, SiCH2CH2), 1 ,91 (s, 12H, Mes-o-Me), 2,43 (s, 6H, Mes- p-Me), 3,81 (m, 12H, CH3CH20), 4,61 (m, 4H, CH2lmz), 6,63 y 6,93 (2 x d, 3 H,H = 1 ,5 Hz, 2 x 2H, Imz-H4 y H5), 6,81 (s, 4H, m-Mes). RMN 13C{1 H} (CDCI3, 75 MHz): Isómero anti: δ 7,1 (SiCH2), 18,4 (CH3CH2O), 19,4 (Mes-p-Me), 23,9 (SiCH2CH2), 29,7 (Mes-o-Me), 53, 1 (CH2lmz), 58,4 (CH3CH20), 120,8 y 122,7 (Imz-C4 y C5), 128,8 (m-Mes), 136,0 (ipso- Mes), 136,6 (o-Mes), 138,2 (p-Me), 169,7 (Imz-C2). Isómero syn: δ 7,5 (SiCH2), 19,8 (CH3CH2O), 21 ,0 (Mes-p-Me), 24,3 (SiCH2CH2), 29,3 (Mes-o-Me), 53,7 (CH2lmz), 58,4 (CH3CH2O), 121 , 1 y 122,7 (Imz-C4 y C5), 128,7 (m-Mes), 135,5 (/pso-Mes), 135,9 (o-Mes), 137,4 (p-Mes), 169,6 (Imz-C2). IR (KBr): v 3080-3170 (m, arC-H st), 1620 (m, arC=C st), 1590 (s, C=N st), 1380-1450 (m, arC=C st), 1072 (w, Si-O-C st), 943 (w, Si-O-C st), 722- 800 (m, Si-C st), 703 errf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 1064,2414 [M + NH4]+.
(EtO)3Si
Example 20. Preparation of palladium complex ll (Si) 2. Compound ll (Si) 2 was prepared in the same manner as compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (Si) 2 described in Example 14 (0.45 g, 0.81 mmol) and of PdBr 2 (COD) (0.15 g, 0.41 mmol). Complex ll (Si) 2 was obtained as a yellow powdery solid (0.83 g, 97%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (56:44) in equilibrium. Anal. Cale. C 42 H 68 N 4 0 6 Si 2 PdBr 2 (1047.41): C, 48, 16; H, 6.54; N, 5.35%; Found: C, 48.41; H, 6.44; N, 5.41%. 1 H NMR (CDCI 3 , 300 MHz): Anti isomer: 0.47 (m, 4H, SiCH 2 ), 1, 20 (m, 18H, CH 3 CH 2 0), 1, 89 (m, 4H, SiCH 2 CH 2 ), 2.22 (s, 12H, Month-o-Me), 2.33 (s, 6H, Month-p-Me), 3.83 (m, 12H, CH 3 CH 2 0) , 4, 17 (m, 4H, CH 2 lmz), 6.70 and 6.98 (2 xd, 3 H, H = 1.5 Hz, 2 x 2H, Imz-H 4 and H 5 ), 6, 94 (s, 4H, m-Month). Syn isomer: δ 0.73 (m, 4H, SiCH 2 ), 1, 23 (m, 18H, CH 3 CH 2 O), 1, 89 (m, 4H, SiCH 2 CH 2 ), 1, 91 (s , 12H, Month-o-Me), 2.43 (s, 6H, Mes-p-Me), 3.81 (m, 12H, CH 3 CH 2 0), 4.61 (m, 4H, CH 2 lmz), 6.63 and 6.93 (2 xd, 3 H, H = 1.5 Hz, 2 x 2H, Imz-H 4 and H 5 ), 6.81 (s, 4H, m-Month). 13 C { 1 H} NMR (CDCI 3 , 75 MHz): Anti isomer: δ 7.1 (SiCH 2 ), 18.4 (CH 3 CH 2 O), 19.4 (Month-p-Me), 23 , 9 (SiCH 2 CH 2 ), 29.7 (Month-o-Me), 53, 1 (CH 2 lmz), 58.4 (CH 3 CH 2 0), 120.8 and 122.7 (Imz- C 4 and C 5 ), 128.8 (m-Month), 136.0 (ipso-Month), 136.6 (o-Month), 138.2 (p-Me), 169.7 (Imz-C 2 ). Syn isomer: δ 7.5 (SiCH 2 ), 19.8 (CH 3 CH 2 O), 21, 0 (Month-p-Me), 24.3 (SiCH 2 CH 2 ), 29.3 (Month- o-Me), 53.7 (CH 2 lmz), 58.4 (CH 3 CH 2 O), 121, 1 and 122.7 (Imz-C 4 and C 5 ), 128.7 (m-Month) , 135.5 (/ pso-Month), 135.9 (o-Month), 137.4 (p-Month), 169.6 (Imz-C 2 ). IR (KBr): v 3080-3170 (m, arC-H st), 1620 (m, arC = C st), 1590 (s, C = N st), 1380-1450 (m, arC = C st), 1072 (w, Si-OC st), 943 (w, Si-OC st), 722-800 (m, Si-C st), 703 errf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 1064.2414 [M + NH 4 ] + . (EtO) 3 Yes
ll(Si)2 ll (Yes) 2
Ejemplo 21. Preparación del complejo de paladio ll(Si)3. El compuesto ll(Si)3 se preparó como se ha descrito para el compuesto ll(Si)1 del Ejemplo 19, partiendo del carbeno de plata 3(Si)3 descrito en el Ejemplo 15 (0,44 g, 0,70 mmol) y de PdBr2(COD) (0,13 g, 0,35 mmol). El complejo ll(Si)3 se obtuvo como un sólido pulverulento de color amarillo (0,75 g, 95%), cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (60:40) en equilibrio. Anal. Cale. C48H8oN406Si2PdBr2 (1131 ,57): C, 50,95; H, 7,13; N, 4,95%; Encontrado: C, 50,86; H 6,63; N 5,07%. RMN 1H (DMSO-d6, 300 MHz): Isómero anti: δ 0,49 (m, 4H, SiCH2), 1 ,13 (m, 42H, CH(CH3)2, CH3CH20), 1 ,89 (m, 4H, SiCH2CH2), 2,45 (m, 4H, CH(CH3)2), 3,72 (m, 12H, CH3CH20), 4,07 (m, 4H, CH2lmz), 7,15-7,80 (m, 10H, Imz-H4 y H5, p-Ph, m-Ph). Isómero syn: 50,58 (m, 4H, SiCH2), 1 ,13 (m, 42H, CH(CH3)2, CH3CH20), 1 ,89 (m, 4H, SiCH2CH2), 2,45 (m, 4H, CH(CH3)2), 3,72 (m, 12H, CH3CH20), 4,20 (m, 4H, CH2lmz), 7,15-7,80 (m, 10H, Imz-H4 y H5, p-Ph, m-Ph). RMN 13C{1H} (DMSO-d6, 75 MHz): δ 8,7 (SiCH2), 14,6 (CH3CH20), 23,1 (SiCH2CH2), 23,6 (CH(CH3)2), 27,3 (CH(CH3)2), 52,6 (CH2lmz), 57,4 (CH3CH20), 121 ,1 y 122,2 (Imz-C4 y C5), 123,4 (p-Ph), 129,6 (m-Ph), 134,1 (/pso-Ph), 144,4 (o-Ph). IR (KBr): v 3030-3120 (m, arC-H st), 1625 (m, arC=C st), 1512 (s, C=N st), 1330-1500 (m, arC=C st), 1123 (w, Si-O-C st), 946 (w, Si-O-C st), 700- 800 (m, Si-C st), 685 errf1 (m, Si-0 st). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 899,3888 [M - 4EtOH - Br + MeOH], 856,1127 [M - 5EtOH - Br + NH4OH]+, 776,1865 [M - 6EtOH - Br]+. Example 21. Preparation of palladium complex ll (Si) 3. Compound ll (Si) 3 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (Si) 3 described in Example 15 (0.44 g, 0.70 mmol ) and PdBr 2 (COD) (0.13 g, 0.35 mmol). Complex ll (Si) 3 was obtained as a yellow powdery solid (0.75 g, 95%), whose structure in solution corresponds to the presence of the trans-syn and trans-anti rotamers (60:40) in equilibrium. Anal. Cale. C 48 H 8 oN 4 0 6 Si 2 PdBr 2 (1131, 57): C, 50.95; H, 7.13; N, 4.95%; Found: C, 50.86; H 6.63; N 5.07%. 1 H NMR (DMSO-d 6 , 300 MHz): Anti isomer: δ 0.49 (m, 4H, SiCH 2 ), 1, 13 (m, 42H, CH (CH 3 ) 2 , CH 3 CH 2 0) , 1, 89 (m, 4H, SiCH 2 CH 2 ), 2.45 (m, 4H, CH (CH 3 ) 2 ), 3.72 (m, 12H, CH 3 CH 2 0), 4.07 ( m, 4H, CH 2 lmz), 7.15-7.80 (m, 10H, Imz-H 4 and H 5 , p-Ph, m-Ph). Syn isomer: 50.58 (m, 4H, SiCH 2 ), 1, 13 (m, 42H, CH (CH 3 ) 2 , CH 3 CH 2 0), 1, 89 (m, 4H, SiCH 2 CH 2 ) , 2.45 (m, 4H, CH (CH 3 ) 2 ), 3.72 (m, 12H, CH 3 CH 2 0), 4.20 (m, 4H, CH 2 lmz), 7.15-7 , 80 (m, 10H, Imz-H 4 and H 5 , p-Ph, m-Ph). 13 C NMR { 1 H} (DMSO-d 6 , 75 MHz): δ 8.7 (SiCH 2 ), 14.6 (CH 3 CH 2 0), 23.1 (SiCH 2 CH 2 ), 23.6 (CH (CH 3 ) 2 ), 27.3 (CH (CH 3 ) 2 ), 52.6 (CH 2 lmz), 57.4 (CH 3 CH 2 0), 121, 1 and 122.2 (Imz -C 4 and C 5 ), 123.4 (p-Ph), 129.6 (m-Ph), 134.1 (/ pso-Ph), 144.4 (o-Ph). IR (KBr): v 3030-3120 (m, arC-H st), 1625 (m, arC = C st), 1512 (s, C = N st), 1330-1500 (m, arC = C st), 1123 (w, Si-OC st), 946 (w, Si-OC st), 700-800 (m, Si-C st), 685 errf 1 (m, Si-0 st). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 899.3888 [M-4EtOH-Br + MeOH], 856.1127 [M-5EtOH-Br + NH 4 OH] + , 776.1865 [M-6 EtOH-Br] + .
ll(S¡)3 ll (Yes) 3
Ejemplo 22. Preparación del complejo de paladio ll(A)1.
El compuesto ll(A)1 se preparó como se ha descrito para el compuesto ll(Si)1 del Ejemplo 19, partiendo del carbeno de plata 3(A)1 descrito en el Ejemplo 16 (1 ,00 g, 3,2 mmol) y de PdBr2(COD) (0,60 g, 1 ,6 mmol). El complejo ll(A)1 se obtuvo como un sólido amarillo aceitoso (0,70 g, 85%), cuya caracterización por RMN requirió su transformación en la sal de amonio, [ll(A)1]2+, por tratamiento con un exceso de NH4CI y cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (30:70) en equilibrio. Anal. Cale. Ci2H22N6PdBr2 (516,57): C, 27,90; H, 4,29; N, 16,27%; Encontrado: C, 28, 10; H 4,76; N, 16,05 %. RMN 1 H (DMSO-d6, 300 MHz, [ll(A)1]2+): Isómero anti: δ 2,88 (t, 3 H,H = 5,6 Hz, 4H, CH2lmz), 3,83 (s, 6H, Imz-Me), 4,08 (t, 3 H,H = 5,6 Hz, 4H, NH2CH2), 7,67 y 7,70 (2 x s, 2 χ 2H, Imz-H4 y H5). Isómero syn: δ 2,88 (t, 3JH,H = 5,6 Hz, 4H, CH2lmz), 3,74 (s, 6H, Imz-Me), 4,24 (t, 3JH,H = 5,6 Hz, 4H, NH2CH2), 7,40 y 7,43 (2 x s, 2 χ 2H, Imz-H4 y H5). RMN 13C{1 H} (DMSO-d6, 75 MHz, [ll(A)1]2+): Isómero anti: δ 37,6 (Imz-Me), 40,8 (CH2lmz), 51 ,5 (NH2CH2), 122,0 y 122,8 (Imz-C4 y C5), 177,8 (Imz-C2). gHMBC-{1 H, 15N} (CDCI3, 293K): S -190 (A/,mz), -198 (A/,mz), -345 (Λ/Η2). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 453, 1629 [M - HBr + NH4]+, 436,1562 [M - Br]+, 355,0865 [M -HBr - Br]+. f=\ Example 22. Preparation of the palladium complex ll (A) 1. Compound ll (A) 1 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 1 described in Example 16 (1, 00 g, 3.2 mmol ) and PdBr 2 (COD) (0.60 g, 1.6 mmol). Complex ll (A) 1 was obtained as an oily yellow solid (0.70 g, 85%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 1] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (30:70) rotamers in equilibrium. Anal. Cale. Ci 2 H22N 6 PdBr 2 (516.57): C, 27.90; H, 4.29; N, 16.27%; Found: C, 28, 10; H, 4.76; N, 16.05%. 1 H NMR (DMSO-d 6 , 300 MHz, [ll (A) 1] 2+ ): Anti isomer: δ 2.88 (t, 3 H , H = 5.6 Hz, 4H, CH 2 lmz), 3.83 (s, 6H, Imz-Me), 4.08 (t, 3 H , H = 5.6 Hz, 4H, NH 2 CH 2 ), 7.67 and 7.70 (2 xs, 2 χ 2H, Imz-H 4 and H 5 ). Syn isomer: δ 2.88 (t, 3 J H , H = 5.6 Hz, 4H, CH 2 lmz), 3.74 (s, 6H, Imz-Me), 4.24 (t, 3 J H , H = 5.6 Hz, 4H, NH 2 CH 2 ), 7.40 and 7.43 (2 xs, 2 χ 2H, Imz-H 4 and H 5 ). 13 C { 1 H} NMR (DMSO-d 6 , 75 MHz, [ll (A) 1] 2+ ): Anti isomer: δ 37.6 (Imz-Me), 40.8 (CH 2 lmz), 51 , 5 (NH 2 CH 2 ), 122.0 and 122.8 (Imz-C 4 and C 5 ), 177.8 (Imz-C 2 ). gHMBC- { 1 H, 15 N} (CDCI 3 , 293K): S -190 (A /, mz ), -198 (A /, mz ), -345 (Λ / Η 2 ). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 453, 1629 [M-HBr + NH 4 ] + , 436.1562 [M-Br] + , 355.0865 [M - HBr - Br] + . f = \
H,N H, N
Br-Pd-Br Br-Pd-Br
- NH, - NH,
\=J \ = J
ll(A)1 ll (A) 1
Ejemplo 23. Preparación del complejo de paladio ll(A)2. Example 23. Preparation of the palladium complex ll (A) 2.
El compuesto ll(A)2 se preparó como se ha descrito para el compuesto ll(Si)1 del Ejemplo 19, partiendo del carbeno de plata 3(A)2 descrito en el Ejemplo 17 (0,50 g, 1 ,2 mmol) y de PdBr2(COD) (0,22 g, 0,60 mmol). El complejo ll(A)2 se obtuvo como un sólido amarillo aceitoso (0,38 g, 88%), cuya caracterización por RMN requirió su transformación en la sal de amonio, [ll(A)2]2+, por tratamiento con un exceso de NH4CI y cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (20:80) en equilibrio. Anal. Cale. C28H38N6PdBr2 (724,87): C, 46,39; H, 5,28; N, 11 ,59%; Encontrado: C, 46,44; H, 5,78; N, 11 ,59%. RMN 1 H (DMSO-d6, 300 MHz, [ll(A)2]2+): Isómero anti: δ 1 ,85 (s, 12H, Mes-o-Me), 2,32 (s, 6H, Mes-p-Me), 2,93 (t, 3JH,H = 5,8 Hz,
4H , CH2lmz), 4, 12 (t, 3 H,H = 5,8 Hz, 4H , N H2CH2), 7,02 (s, 4H , m-Mes), 7,44 y 7,67 (2 x d, 3JH,H = 1 , 8 Hz, 2 x 2H , lmz-H4 y H5). Isómero syn: δ 1 ,91 (s, 12H , Mes-o-Me), 2,36 (s, 6H , Mes-p-Me), 2,96 (t, 3JH,H = 5,8 Hz, 4H , CH2lmz), 4, 19 (t, 3JH,H = 5,8 Hz, 4H , N H2CH2), 6,92 (s, 4H , m-Mes), 7,36 y 7,62 (2 x d, 3JH,H = 1 ,7 HZ, 2 χ 2H , lmz-H4 y H5). RMN 13C{1 H} (DMSO-d6, 75 MHz, [ll(A)2]2+): Isómero anti: δ 16,7 (Mes-p-Me), 20, 1 (Mes-o-Me), 43,4 (CH2lmz), 53,6 (NH2CH2), 121 ,9 y 122,5 (lmz-C4 y C5), 128,4 (m-Mes), 128,7 (ipso- Mes), 134,0 (o-Mes), 137,9 (p-Mes), 171 ,5 (Imz-C2). gHMBC-{1 H, 15N} (CDCI3, 293K): δ -191 (Λ/imz), -192 (A/,mz), -368 (Λ/Η2). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 644,9697 [M - Br]+, 563,2124 [M - Br - HBr]+. Compound ll (A) 2 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 2 described in Example 17 (0.50 g, 1.2 mmol ) and PdBr 2 (COD) (0.22 g, 0.60 mmol). Complex ll (A) 2 was obtained as an oily yellow solid (0.38 g, 88%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 2] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (20:80) rotamers in equilibrium. Anal. Cale. C 28 H 3 8N 6 PdBr 2 (724.87): C, 46.39; H, 5.28; N, 11, 59%; Found: C, 46.44; H, 5.78; N, 11, 59%. 1 H NMR (DMSO-d 6 , 300 MHz, [ll (A) 2] 2+ ): Anti isomer: δ 1.85 (s, 12H, Mes-o-Me), 2.32 (s, 6H, Month-p-Me), 2.93 (t, 3 J H , H = 5.8 Hz, 4H, CH 2 lmz), 4, 12 (t, 3 H, H = 5.8 Hz, 4H, NH 2 CH 2 ), 7.02 (s, 4H, m-Month), 7.44 and 7, 67 (2 xd, 3 JH , H = 1, 8 Hz, 2 x 2H, lmz-H 4 and H 5 ). Syn isomer: δ 1, 91 (s, 12H, Month-o-Me), 2.36 (s, 6H, Month-p-Me), 2.96 (t, 3 J H, H = 5.8 Hz , 4H, CH 2 lmz), 4, 19 (t, 3 J H, H = 5.8 Hz, 4H, NH 2 CH 2 ), 6.92 (s, 4H, m-Month), 7.36 and 7.62 (2 xd, 3 J H, H = 1, 7 HZ, 2 χ 2H, lmz-H 4 and H 5 ). 13 C NMR { 1 H} (DMSO-d 6 , 75 MHz, [ll (A) 2] 2+ ): Anti isomer: δ 16.7 (Month-p-Me), 20, 1 (Month-o- Me), 43.4 (CH 2 lmz), 53.6 (NH 2 CH 2 ), 121, 9 and 122.5 (lmz-C 4 and C 5 ), 128.4 (m-Month), 128, 7 (ipso-Month), 134.0 (o-Month), 137.9 (p-Month), 171, 5 (Imz-C 2 ). gHMBC- { 1 H, 15 N} (CDCI 3 , 293K): δ -191 (Λ / imz), -192 (A /, mz ), -368 (Λ / Η 2 ). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 644.9697 [M-Br] + , 563.2124 [M-Br-HBr] + .
ll(A)2 ll (A) 2
Ejemplo 24. Preparación del complejo de paladio ll(A)3. El compuesto ll(A)3 se preparó como se ha descrito para el compuesto ll(Si)1 del Ejemplo 19, partiendo del carbeno de plata 3(A)3 descrito en el Ejemplo 18 (0,50 g, 0,85 mmol) y de PdBr2(COD) (0, 16 g, 0,42 mmol). El complejo ll(A)3 se obtuvo como un sólido amarillo aceitoso (0,58 g, 84%), cuya caracterización por RMN requirió su transformación en la sal de amonio, [ll(A)3]2+, por tratamiento con un exceso de NH4CI y cuya estructura en disolución se corresponde con la presencia de los rotámeros trans-syn y trans-anti (25:75) en equilibrio. Anal. Cale. C34H5oN6PdBr2 (809,03): C, 50,48; H, 6,23; N, 10,39%; Encontrado: C, 50,07; H, 5,98; N, 10, 13%. 1 H NMR (DMSO-d6, 300 MHz, [ll(A)3]2+): Isómero anti: δ 1 ,07 (d, 3 H,H = 6,9 Hz, 24H, CH(CH3)2), 2,26 (sep., 3JH,H = 6,9 Hz, 4H, CH(CH3)2), 2,89 (m, 4H, CH2lmz), 4,08 (m, 4H, NH2CH2), 7,32 (d, 3JH,H = 7,9 Hz, 4H, m- Ph), 7,49 (t, 3JH,H = 7,9 Hz, 2H, p-Ph), 7,61 y 7,71 (2 x d, 3JH,H = 1 ,6 HZ, 2 χ 2H, Imz-H4 y H5). Isómero syn: δ 1 ,12 (d, 3JH,H = 6,9 Hz, 24H, CH(CH3)2), 2,26 (sep., 3JH,H = 6,9 Hz, 4H, CH(CH3)2), 2,99 (m, 4H, CH2lmz), 4,22 (m, 4H, NH2CH2), 7,32 (d, 3JH,H = 7,7 Hz, 4H, m- Ph), 7,45 (t, 3JH,H = 7,7 Hz, 2H, p-Ph), 7,59 y 7,67 (2 x d, 3JH,H = 1 ,5 HZ, 2 χ 2H, Imz-H4 y H5). 13C{1 H} NMR (DMSO-d6, 75 MHz, [ll(A)3]2+): Isómero anti: 5 23,3 (CH(CH3)2), 23,6 CH(CH3)2), 27,2 (CH(CH3)2), 42,5 (CH2lmz), 53,5 (NH2CH2), 121 ,9 y 123,9 (Imz-C4 y C5), 123,4 (m-Ph), 129,5 (/pso-Ph), 134,5 (o-Ph), 144,9 (p-Ph), 181 ,3 (Imz-C2). gHMBC-{1 H,
15N} (CDCI3, 293K): δ -187 (A/,mz), -205 (A/,mz), -377 (Λ/Η2). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 837,3255 [M - Br + HCOOH + HCOONH4]+, 755,4001 [M - 2HBr + 2HCOOH + NH4]+. Example 24. Preparation of the palladium complex ll (A) 3. Compound ll (A) 3 was prepared as described for compound ll (Si) 1 of Example 19, starting from the silver carbine 3 (A) 3 described in Example 18 (0.50 g, 0.85 mmol ) and PdBr 2 (COD) (0.16 g, 0.42 mmol). Complex ll (A) 3 was obtained as an oily yellow solid (0.58 g, 84%), whose NMR characterization required its transformation into the ammonium salt, [ll (A) 3] 2+ , by treatment with an excess of NH 4 CI and whose structure in solution corresponds to the presence of the trans-syn and trans-anti (25:75) rotamers in equilibrium. Anal. Cale. C 34 H 5 or 6 PdBr 2 (809.03): C, 50.48; H, 6.23; N, 10.39%; Found: C, 50.07; H, 5.98; N, 10, 13%. 1 H NMR (DMSO-d 6 , 300 MHz, [ll (A) 3] 2+ ): Anti isomer: δ 1, 07 (d, 3 H, H = 6.9 Hz, 24H, CH (CH 3 ) 2 ), 2.26 (sep., 3 J H, H = 6.9 Hz, 4H, CH (CH 3 ) 2 ), 2.89 (m, 4H, CH 2 lmz), 4.08 (m, 4H, NH 2 CH 2 ), 7.32 (d, 3 J H, H = 7.9 Hz, 4H, m- Ph), 7.49 (t, 3 J H, H = 7.9 Hz, 2H , p-Ph), 7.61 and 7.71 (2 xd, 3 J H, H = 1, 6 HZ, 2 χ 2H, Imz-H 4 and H 5 ). Syn isomer: δ 1, 12 (d, 3 J H, H = 6.9 Hz, 24H, CH (CH 3 ) 2 ), 2.26 (Sep., 3 J H, H = 6.9 Hz, 4H , CH (CH 3 ) 2 ), 2.99 (m, 4H, CH 2 lmz), 4.22 (m, 4H, NH 2 CH 2 ), 7.32 (d, 3 J H, H = 7, 7 Hz, 4H, m- Ph), 7.45 (t, 3 J H, H = 7.7 Hz, 2H, p-Ph), 7.59 and 7.67 (2 xd, 3 J H, H = 1.5 HZ, 2 χ 2H, Imz-H 4 and H 5 ). 13 C { 1 H} NMR (DMSO-d 6 , 75 MHz, [ll (A) 3] 2+ ): Anti isomer: 5 23.3 (CH (CH 3 ) 2 ), 23.6 CH (CH 3 ) 2 ), 27.2 (CH (CH 3 ) 2 ), 42.5 (CH 2 lmz), 53.5 (NH 2 CH 2 ), 121, 9 and 123.9 (Imz-C 4 and C 5 ), 123.4 (m-Ph), 129.5 (/ pso-Ph), 134.5 (o-Ph), 144.9 (p-Ph), 181, 3 (Imz-C 2 ). gHMBC- { 1 H, 15 N} (CDCI 3 , 293K): δ -187 (A /, mz ), -205 (A /, mz ), -377 (Λ / Η 2 ). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 837.3255 [M - Br + HCOOH + HCOONH 4 ] + , 755.4001 [M - 2HBr + 2HCOOH + NH 4 ] + .
ll(A)3 ll (A) 3
Ejemplo 25. Preparación de la sal de imidazolio 4.4. Example 25. Preparation of the imidazolium salt 4.4.
En una ampolla de 25 mL se colocó el bis(imidazolil)metano de partida (0,26 g, 1 ,7 mmol) y la N-(2-bromoetil)ftalimida (1 , 11 g, 4,4 mmol). Después de someter los sólidos a vacío durante 5 min, se disolvieron en 5 mL de CH3CN seco y se calentó la disolución resultante a 120 °C durante 48 h. Tras filtrar y secar el sólido, se obtuvo la sal 4.4 como un sólido pulverulento de color blanco (1 ,05 g, 91 %). Anál. Cale, para C27H24N604Br2-2H20 (692,36): C, 46,84; H, 4,08; N, 12, 14%; Encontrado: C, 47,03; H, 4,01 ; N , 12,03%. RMN 1 H (DMSO-d6, 300 MHz): δ 3,99 (t, 3 H,H = 4,6 Hz, 4H, CH2ftal), 4,53 (t, 3JH,H = 4,6 Hz, 4H, CH2lmz), 6,71 (s, 2H, CH2), 7,82 (s, 8H, o-ftal, m-ftal), 7,92 y 8,02 (2 x s, 2 x 2H, Imz-H4 y H5), 9,56 (s, 2H, Imz-H2). RMN 13C{1 H} (DMSO-d6, 75 MHz): δ 37,4 (CH2ftal), 47,9 (CH2lmz), 57,8 (CH2), 121 ,5 y 123,4 (Imz-C4 y C5), 122,7 (o-ftal), 131 ,0 (/pso-ftal), 134,1 (m-ftal), 137,6 (Imz-C2), 167,2 (C=0). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 495, 1763 [M - HBr - Br]+. In a 25 mL ampoule, the starting bis (imidazolyl) methane (0.26 g, 1.7 mmol) and the N- (2-bromoethyl) phthalimide (1.1 g, 4.4 mmol) were placed. After the solids were subjected to vacuum for 5 min, they were dissolved in 5 mL of dry CH 3 CN and the resulting solution was heated at 120 ° C for 48 h. After filtering and drying the solid, salt 4.4 was obtained as a white powdery solid (1.05 g, 91%). Anal. Cale, for C 27 H 24 N 6 0 4 Br 2 -2H 2 0 (692.36): C, 46.84; H, 4.08; N, 12, 14%; Found: C, 47.03; H, 4.01; N, 12.03%. 1 H NMR (DMSO-d 6 , 300 MHz): δ 3.99 (t, 3 H, H = 4.6 Hz, 4H, CH 2 ftal), 4.53 (t, 3 J H, H = 4 , 6 Hz, 4H, CH 2 lmz), 6.71 (s, 2H, CH 2 ), 7.82 (s, 8H, o-ftal, m-ftal), 7.92 and 8.02 (2 xs , 2 x 2H, Imz-H 4 and H 5 ), 9.56 (s, 2H, Imz-H 2 ). 13 C { 1 H} NMR (DMSO-d 6 , 75 MHz): δ 37.4 (CH 2 ftal), 47.9 (CH 2 lmz), 57.8 (CH 2 ), 121, 5 and 123, 4 (Imz-C 4 and C 5 ), 122.7 (o-ftal), 131, 0 (/ pso-ftal), 134.1 (m-ftal), 137.6 (Imz-C 2 ), 167 , 2 (C = 0). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 495, 1763 [M-HBr-Br] + .
4.4 4.4
Ejemplo 26. Preparación del complejo quelato de paladio 5.4.
En una ampolla de 15 mL con tapa roscada se pesó la sal de bisimidazolio 4.4 descrita en el Ejemplo 25 (0,50 g, 0,76 mmol) y se disolvió en 1 mL de DMSO, sobre esa disolución se añadió un equivalente de acetato de paladio (0,17 g, 0,76 mmol). La suspensión resultante se calentó a 50 °C con agitación durante 2 h. Tras estas 2 h, se subió progresivamente la temperatura hasta 1 10 °C a lo largo de 3 h. La disolución rojiza resultante se pasó a través de una columna de celite de unos 2,0 cm de altura y 1 ,5 cm de diámetro. Tras evaporar el DMSO y secar el sólido, se obtuvo el carbeno quelato de paladio 5.4 como un sólido de color gris (0,49 g, 85%). Anál. Cale, para C27H22N604PdBr2 H20 (778,74): C, 41 ,64; H, 3,1 1 ; N, 10,79%; Encontrado: C, 41 ,48; H, 3,23; N, 10,95%. RMN 1 H (DMSO-d6, 300 MHz): 5 3,80-4, 10 (2 x m, 2 χ 2H, CH2ftal), 4, 11 y 5, 15 (2 x m, 2 x 2H, CH2lmz), 6,25 (m, 2H, CH2), 7,33 y 7,52 (2 x s, 2 χ 1 H, Imz-H4 y H5), 7,60 (s, 8H, o-ftal y m-ftal). RMN 13C{1 H} (DMSO-d6, 75 MHz): 5 37,5 (CH2ftal), 48,5 (CH2lmz), 62, 1 (CH2), 120,8 y 121 ,3 (Imz-C4 y C5), 122,3 (o-ftal), 130,7 (/pso-ftal), 133,6 (m-ftal), 159,6 (Imz-C2), 166,7 (C=0). MS (ESlVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 761 ,039 [M + H]+, 697, 126 [M - HBr+ NH4]+, 617,086 [M - 2HBr + NH4]+. Example 26. Preparation of palladium chelate complex 5.4. The bisimidazolium salt 4.4 described in Example 25 (0.50 g, 0.76 mmol) was weighed in a 15 mL ampoule with screw cap and dissolved in 1 mL of DMSO, an equivalent of acetate was added to that solution palladium (0.17 g, 0.76 mmol). The resulting suspension was heated at 50 ° C with stirring for 2 h. After these 2 h, the temperature was gradually increased to 1 10 ° C over 3 h. The resulting reddish solution was passed through a celite column about 2.0 cm high and 1.5 cm in diameter. After evaporating the DMSO and drying the solid, palladium carbonate chelate 5.4 was obtained as a gray solid (0.49 g, 85%). Anal. Cale, for C 27 H 22 N 6 0 4 PdBr 2 H 2 0 (778.74): C, 41, 64; H, 3.1 1; N, 10.79%; Found: C, 41, 48; H, 3.23; N, 10.95%. 1 H NMR (DMSO-d 6 , 300 MHz): 5 3.80-4, 10 (2 xm, 2 χ 2H, CH 2 ftal), 4, 11 and 5, 15 (2 xm, 2 x 2H, CH 2 lmz), 6.25 (m, 2H, CH 2 ), 7.33 and 7.52 (2 xs, 2 χ 1 H, Imz-H 4 and H 5 ), 7.60 (s, 8H, or -ftal and m-ftal). 13 C { 1 H} NMR (DMSO-d 6 , 75 MHz): 5 37.5 (CH 2 ftal), 48.5 (CH 2 lmz), 62, 1 (CH 2 ), 120.8 and 121, 3 (Imz-C 4 and C 5 ), 122.3 (o-ftal), 130.7 (/ pso-ftal), 133.6 (m-ftal), 159.6 (Imz-C 2 ), 166 , 7 (C = 0). MS (ESlVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 761, 039 [M + H] + , 697, 126 [M - HBr + NH 4 ] + , 617,086 [M - 2HBr + NH 4 ] + .
5.4 5.4
Ejemplo 27. Preparación del complejo quelato de paladio lll(A)4. Example 27. Preparation of palladium chelate complex lll (A) 4.
En una ampolla de 25 mL se pesó el complejo de paladio 5.4 descrito en el Ejemplo 26 (1 ,00 g, 1 ,3 mmol) y se disolvió en 2 mL de CH3CN seco. Sobre la suspensión formada, se añadieron 40 equivalentes de hidrazina (2,50 mL, 52,0 mmol), dando una disolución transparente. Tras una hora de reacción a temperatura ambiente, se filtró la ftalilhidracina formada, se evaporó el disolvente y se lavó con THF caliente utilizando un equipo soxhlet, obteniéndose el producto lll(A)4 como un sólido beis (0,50 g, 82%). Anal. Cal. para Cn H20N6OPdBr2 H2O (518,54): C, 25,48; H, 3,89; N, 16,21 %; Encontrado C, 25,46; H, 4,02; N, 16,23%. RMN 1 H (DMSO-d6, 300 MHz): 5 3,03 (s ancho, 4H, CH2lmz), 4,23 (s ancho, 4H, NH2CH2), 4,70 (s ancho, 4H, NH2), 6,34 (s, 2H, CH2), 7,62 y 7,69 (2 x s , 2 x 1 H, Imz-H4 y H5). RMN 13C{1 H} (DMSO-d6, 75 MHz): δ 40,3 (CH2lmz), 49,3 (NH2CH2),
61 ,3 (CH2), 120,6 y 122,7 (Imz-C4 y C5), 152,0 (Imz-C2). gHMBC-{1 H, 15N} (DMSO-d6, 293K): δ -197 (A/,mz), -203 (A/,mz), -381 (Λ/Η2). IR (KBr): v 3393 (NH2 st), 3030-3100 (m, arC-H st), 1590-1610 (m, arC=C st), 1530 (s, C=N st), 1395-1480 crrf1 (m, arC=C st). MS (ESIVTOF, CH2CI2/MeOH/NH4HCOO 5 mM): m/z 420,9814 [M - Br]+, 365,1714 [M - 2HBr + Na]+, 339,0556 [M - HBr- Br]+. The palladium 5.4 complex described in Example 26 (1.00 g, 1.3 mmol) was weighed in a 25 mL ampoule and dissolved in 2 mL of dry CH 3 CN. On the suspension formed, 40 equivalents of hydrazine (2.50 mL, 52.0 mmol) were added, giving a clear solution. After one hour of reaction at room temperature, the phthalyhydhydrazine formed was filtered, the solvent was evaporated and washed with hot THF using a soxhlet kit, the product lll (A) 4 being obtained as a beige solid (0.50 g, 82% ). Anal. Cal. For Cn H 20 N 6 OPdBr 2 H 2 O (518.54): C, 25.48; H, 3.89; N, 16.21%; Found C, 25.46; H, 4.02; N, 16.23%. 1 H NMR (DMSO-d 6 , 300 MHz): 5 3.03 (wide s, 4H, CH 2 lmz), 4.23 (wide s, 4H, NH 2 CH 2 ), 4.70 (wide s, 4H, NH 2 ), 6.34 (s, 2H, CH 2 ), 7.62 and 7.69 (2 xs, 2 x 1 H, Imz-H 4 and H 5 ). 13 C NMR { 1 H} (DMSO-d 6 , 75 MHz): δ 40.3 (CH 2 lmz), 49.3 (NH 2 CH 2 ), 61, 3 (CH 2 ), 120.6 and 122.7 (Imz-C 4 and C 5 ), 152.0 (Imz-C 2 ). gHMBC- { 1 H, 15 N} (DMSO-d 6 , 293K): δ -197 (A /, mz ), -203 (A /, mz ), -381 (Λ / Η 2 ). IR (KBr): v 3393 (NH 2 st), 3030-3100 (m, arC-H st), 1590-1610 (m, arC = C st), 1530 (s, C = N st), 1395-1480 crrf 1 (m, arC = C st). MS (ESIVTOF, CH 2 CI 2 / MeOH / NH 4 HCOO 5 mM): m / z 420.9814 [M-Br] + , 365.1714 [M-2HBr + Na] + , 339.0556 [M - HBr - Br] + .
III(A)4 III (A) 4
BIBLIOGRAFÍA BIBLIOGRAPHY
"Guideline on the Specification Limits for Residues of Metal Catalyst or Metal Reagents", European Medicines Agency, 2008, Doc. Ref. EMEA/CHMP/SWP/4446/2000. de Vries, J. G. "Palladium-Catalysed Coupling Reactions", Top. Organomet. Chem. 2012, 42, 1-34. "Guideline on the Specification Limits for Residues of Metal Catalyst or Metal Reagents", European Medicines Agency, 2008, Doc. Ref. EMEA / CHMP / SWP / 4446/2000. de Vries, J. G. "Palladium-Catalysed Coupling Reactions", Top. Organomet Chem. 2012, 42, 1-34.
Diez-González, S.; Marión, N.; Nolan, S. P. "N-Heterocyclic Carbenes in Late Transition Metal Catalysis", Chem. Rev. 2009, 109, 3612-3676. Baig, R. B. N; Varma; R. S. "Magnetically retrievable catalysts for organic synthesis", Chem. Commun. 2013, 49, 752-770. Ten-González, S .; Marion, N .; Nolan, S. P. "N-Heterocyclic Carbenes in Late Transition Metal Catalysis", Chem. Rev. 2009, 109, 3612-3676. Baig, R. B. N; Varma; R. S. "Magnetically retrievable catalysts for organic synthesis", Chem. Commun. 2013, 49, 752-770.
Shylesh, S.; Schünemann, V.; Thiel, W. R. "Magnetically Separable Nanocatalysts: Shylesh, S .; Schünemann, V .; Thiel, W. R. "Magnetically Separable Nanocatalysts:
Bridges between Homogeneous and Heterogeneous Catalysis", Angew. Chem. Int. Ed. 2010, 49, 3428-3459. Bridges between Homogeneous and Heterogeneous Catalysis ", Angew. Chem. Int. Ed. 2010, 49, 3428-3459.
Stevens, P. D.; Li, G.; Fan, J.; Yen, M.; Gao, Y. "Recycling of homogeneous Pd catalysis using superparamagnetic nanoparticles as novel soluble supports for Suzuki, Heck, and Sonogashira cross-coup ing reactions", Chem. Commun. 2005, 4435-4437. Stevens, P. D .; Li, G .; Fan, J .; Yen, M .; Gao, Y. "Recycling of homogeneous Pd catalysis using superparamagnetic nanoparticles as novel soluble supports for Suzuki, Heck, and Sonogashira cross-coup ing reactions", Chem. Commun. 2005, 4435-4437.
Zheng, Y; Stevens, P. D.; Gao, Y. "Magnetic Nanoparticles as an Orthogonal Support of Polymer Resins: Applications to Solid-Phase Suzuki Cross-Coupling Reactions", J. Org.
Chem. 2006, 71, 537-542. Zheng, Y; Stevens, PD; Gao, Y. "Magnetic Nanoparticles as an Orthogonal Support of Polymer Resins: Applications to Solid-Phase Suzuki Cross-Coupling Reactions", J. Org. Chem. 2006, 71, 537-542.
Stevens, P. D.; Li, G.; Gardimalla, H. M. R.; Yen, M.; Gao, Y. "Superparamagnetic Stevens, P. D .; Li, G .; Gardimalla, H. M. R .; Yen, M .; Gao, Y. "Superparamagnetic
Nanoparticle-Supported Catalysis of Suzuki Cross-Coupling Reactions", Org. Lett. 2005, 7, 2085-2088. Nanoparticle-Supported Catalysis of Suzuki Cross-Coupling Reactions ", Org. Lett. 2005, 7, 2085-2088.
Yang, H.; Li, G.; Ma, Z. "Magnetic core-shell-structured nanoporous organosilica microspheres for the Suzuki-Miyaura coupling of aryl chlorides: improved catalytic activity and facile catalyst recovery", J. Mater. Chem. 2012, 22, 6639-6648. Yang, H .; Li, G .; Ma, Z. "Magnetic core-shell-structured nanoporous organosilica microspheres for the Suzuki-Miyaura coupling of aryl chlorides: improved catalytic activity and facile catalyst recovery", J. Mater. Chem. 2012, 22, 6639-6648.
Yang, H.; Wang, Y.; Qin, Y.; Chong, Y.; Yang, Q.; Li, G.; Zhang, L; Li, W. "One-pot preparation of magnetic N-heterocyclic carbene-functionalized silica nanoparticles for the Suzuki-Miyaura coupling of aryl chlorides: improved activity and facile catalyst recovery", Green Chem. 2011 , 13, 1352-1361. Yang, H .; Wang, Y .; Qin, Y .; Chong, Y .; Yang, Q .; Li, G .; Zhang, L; Li, W. "One-pot preparation of magnetic N-heterocyclic carbene-functionalized silica nanoparticles for the Suzuki-Miyaura coupling of aryl chlorides: improved activity and facile catalyst recovery", Green Chem. 2011, 13, 1352-1361.
Tyrrell, E.; Whiteman, L; Williams, N. "The synthesis and characterisation of immobilised palladium carbene complexes and their application to heterogeneous catalysis", J. Tyrrell, E .; Whiteman, L; Williams, N. "The synthesis and characterization of immobilized palladium carbene complexes and their application to heterogeneous catalysis", J.
Organomet. Chem. 2011 , 696, 3465-3472. Martínez-Olid, F. J.; Andrés, R.; de Jesús, E.; Flores, J. C; Heuzé, K.; Vellutini, L. Organomet Chem. 2011, 696, 3465-3472. Martínez-Olid, F. J .; Andrés, R .; of Jesus, E .; Flores, J. C; Heuzé, K .; Vellutini, L.
"Complejos NHC de paladio heterogeneizados y sus usos como catalizadores "NHC heterogeneized palladium complexes and their uses as catalysts
recuperables", Solicitud de Patente Española 2014 (26/06/14), P 201400505. recoverable ", Spanish Patent Application 2014 (06/26/14), P 201400505.
Harjani, J. R.; Friscic, T.; MacGillivray, L. R.; Singer, R. D. "Removal of metal ions from aqueous solutions using chelating task-specific ionic liquids", Dalton Trans. 2008, 4595- 4601. Harjani, J. R .; Friscic, T .; MacGillivray, L. R .; Singer, R. D. "Removal of metal ions from aqueous solutions using chelating task-specific ionic liquids", Dalton Trans. 2008, 4595-4601.
Bussetto, L.; Cassani, M. C; Femoni, C; Macchioni, A.; Mazzoni, R.; Zuccaccia, D. Bussetto, L .; Cassani, M. C; Femoni, C; Macchioni, A .; Mazzoni, R .; Zuccaccia, D.
"Synthesis, molecular structures and solution NMR studies of N-heterocyclic carbene- amine silver complexes", J. Organomet. Chem. 2008, 693, 2579-2591. "Synthesis, molecular structures and solution NMR studies of N-heterocyclic carbene-amine silver complexes", J. Organomet. Chem. 2008, 693, 2579-2591.
Bailarín, B.; Busetto, L.; Cassani, M. C; Femoni, C; Ferrari, A. M.; Miletto, I.; Caputo, G. "Primary amino-functionalize N-heterocyclic carbene ligands as support for Au(i)- - Au(i) interacctions: structural, electrochemical, spectroscopic and computacional studies of the dimolecular [A^CNh^Ch^imMeMNOsk", Dalton Trans. 2012, 41, 2445-2455.
Ohara, H., O, W. W. N.; Lough, A. J.; Morris, R. H. "Effect of chelating ring size in catalytic ketone hydrogenation: facile synthesis of ruthenium(n) precatalysts containing an N- heterocyclic carbene with a primary amine donor for ketone hydrogenation and a DFT study of mechanisms", Dalton Trans. 2012, 41, 8797-8808. Dancer, B .; Busetto, L .; Cassani, M. C; Femoni, C; Ferrari, AM; Miletto, I .; Caputo, G. "Primary amino-functionalize N-heterocyclic carbene ligands as support for Au (i) - - Au (i) interactions: structural, electrochemical, spectroscopic and computational studies of the dimolecular [A ^ CNh ^ Ch ^ imMeMNOsk", Dalton Trans. 2012, 41, 2445-2455. Ohara, H., O, WWN; Lough, AJ; Morris, RH "Effect of chelating ring size in catalytic ketone hydrogenation: facile synthesis of ruthenium (n) precatalysts containing an N- heterocyclic carbene with a primary amine donor for ketone hydrogenation and a DFT study of mechanisms", Dalton Trans. 2012, 41, 8797-8808.
Chi, Y. S.; Lee, J. K.; Lee, S.-g; Choi, I. S. "Control of Wettability by Anión Exchange on Si/Si02 Surfaces", Langmuir 2004, 20, 3024-3027. Chi, YS; Lee, JK; Lee, S.-g; Choi, IS "Control of Wettability by Anion Exchange on Si / Si0 2 Surfaces", Langmuir 2004, 20, 3024-3027.
Trilla, M.; Pleixats.R.; Wong Chi Man; M.; Bied, C. "Organic-inorganic hybrid silica materials containing imidazolium and dihydroimidazolium salts as recyclable Trilla, M .; Pleixats.R .; Wong Chi Man; M .; Bied, C. "Organic-inorganic hybrid silica materials containing imidazolium and dihydroimidazolium salts as recyclable
organocatalysts for Knoevenagel condensations", Green Chem. 2009, 11, 1815-1820. organocatalysts for Knoevenagel condensations ", Green Chem. 2009, 11, 1815-1820.
Borja, G.; Monge-Marcet, A.; Pleixats, R.; Parella, T.; Cattoén, X.; Wong Chi Man, M. "Recyclable Hybrid Silica-Based Catalysts Derived from Pd-NHC Complexes for Suzuki, Heck and Sonogashira Reactions", Eur. J. Org. Chem. 2012, 3625-3635. Borja, G .; Monge-Marcet, A .; Pleixats, R .; Parella, T .; Cattoén, X .; Wong Chi Man, M. "Recyclable Hybrid Silica-Based Catalysts Derived from Pd-NHC Complexes for Suzuki, Heck and Sonogashira Reactions", Eur. J. Org. Chem. 2012, 3625-3635.
Berardi, S.; Carraro, M.; Iglesias, M.; Sartorel, A.; Scorrano, G.; Albrecht, M.; Bonchio, M. "Polyoxometalate-Based N-Heterocyclic Carbene (NHC) Complexes for Palladium- Mediated C-C Coupling and Chloroaryl Dehalogenation Catalysis", Chem. Eur. J. 2010, 16, 10662-1066. Berardi, S .; Carraro, M .; Iglesias, M .; Sartorel, A .; Scorrano, G .; Albrecht, M .; Bonchio, M. "Polyoxometalate-Based N-Heterocyclic Carbene (NHC) Complexes for Palladium-Mediated C-C Coupling and Chloroaryl Dehalogenation Catalysis", Chem. Eur. J. 2010, 16, 10662-1066.
Kunze, K.; Nyce, G.; Guo, W. "Methods of polymerizing silanes and cyclosilanes using N- heterocyclic carbenes, metal complexes having N-heterocyclic carbene ligands, and lanthanide compounds", PCT Int. Appl. 2011 , PCT/US201 1/046155, WO2013019208A1. Kunze, K .; Nyce, G .; Guo, W. "Methods of polymerizing silanes and cyclosilanes using N-heterocyclic carbenes, metal complexes having N-heterocyclic carbene ligands, and lanthanide compounds", PCT Int. Appl. 2011, PCT / US201 1/046155, WO2013019208A1.
Diez-Barra, E.; de la Hoz, A.; Sánchez-Migallón, A.; Tejeda, J. "Phase transfer catalysis without solvent. Synthesis of bisazolylalkanes", Heterocycles 1992, 34, 1365-1373. Ten-Bar, E .; de la Hoz, A .; Sánchez-Migallón, A .; Tejeda, J. "Phase transfer catalysis without solvent. Synthesis of bisazolylalkanes", Heterocycles 1992, 34, 1365-1373.
Organ, M. G.; O'Brien, C. J.; Kantchev, E. A. B. "Transition metal complexes of N- heterocyclic carbenes, method of preparation and use in transition metal catalyzed organic transformations", CA Appl. 2007, CA2556850A1). Organ, M. G .; O'Brien, C. J .; Kantchev, E. A. B. "Transition metal complexes of N-heterocyclic carbenes, method of preparation and use in transition metal catalyzed organic transformations", CA Appl. 2007, CA2556850A1).
Yang, H.; Han, X.; Li, G.; Yunwei Wang, Y. "N-Heterocyclic carbene palladium complex supported on ionic liquid-modified SBA-16: an efficient and highly recyclable catalyst for the Suzuki and Heck reactions", Green Chem. 2009, 11, 1 184-1193.
Polshettiwar, V.; Varma, R. S. "Pd-N-heterocyclic carbene (NHC) organic silica: synthesis and application in carbonecarbon coupling reactions", Tetrahedron 2008, 64, 4637-4643. Yang, H .; Han, X .; Li, G .; Yunwei Wang, Y. "N-Heterocyclic carbene palladium complex supported on ionic liquid-modified SBA-16: an efficient and highly recyclable catalyst for the Suzuki and Heck reactions", Green Chem. 2009, 11, 1 184-1193. Polshettiwar, V .; Varma, RS "Pd-N-heterocyclic carbene (NHC) organic silica: synthesis and application in carbonecarbon coupling reactions", Tetrahedron 2008, 64, 4637-4643.
Corma, A.; González-Arellano, C; Iglesias, M.; Pérez-Ferreras, S.; Sánchez, F. Corma, A .; González-Arellano, C; Iglesias, M .; Pérez-Ferreras, S .; Sánchez, F.
"Heterogenized Gold(l), Gold(lll), and Palladium(ll) Complexes for C-C Bond Reactions", Syntlett 2007, 1771-1774. "Heterogenized Gold (l), Gold (lll), and Palladium (ll) Complexes for C-C Bond Reactions", Syntlett 2007, 1771-1774.
Lee, S.-M.; Yoon, H.-J.; Kim, J.-H.; Chung, W.-J.; Lee, Y.-S. "Highly active organosilane- based N-heterocyclic carbene-palladium complex immobilized on silica partióles for the Suzuki reaction", Puré Appl. Chem. 2007, 79, 1553-1559. Lee, S.-M .; Yoon, H.-J .; Kim, J.-H .; Chung, W.-J .; Lee, Y.-S. "Highly active organosilane-based N-heterocyclic carbene-palladium complex immobilized on silica partiols for the Suzuki reaction", Puré Appl. Chem. 2007, 79, 1553-1559.
Karimi, B.; Enders, D. "New N-Heterocyclic Carbene Palladium Complex/lonic Liquid Matrix Immobilized on Silica: Application as Recoverable Catalyst for the Heck Reaction", Org. Lett. 2006, 8, 1237-1240. Karimi, B .; Enders, D. "New N-Heterocyclic Carbene Palladium Complex / lonic Liquid Matrix Immobilized on Silica: Application as Recoverable Catalyst for the Heck Reaction", Org. Lett. 2006, 8, 1237-1240.
Wang, H. M. J.; Lin, I. J. B. "Facile Synthesis of Silver(l)-Carbene Complexes. Useful Carbene Transfer Agents", Organometallics 1998, 17, 972-975.
Wang, H. M. J .; Lin, I. J. B. "Facile Synthesis of Silver (l) -Carbene Complexes. Useful Carbene Transfer Agents", Organometallics 1998, 17, 972-975.
Claims
REIVINDICACIONES
Compuesto de fórmula 1 caracterizado porque tiene una estructura de sal de imidazolio N-sustituida con una alquilamina primaria protegida en forma de grupo ftalimido, Compound of formula 1 characterized in that it has an N-substituted imidazolium salt structure with a protected primary alkylamine in the form of a phthalimido group,
- un heterociclo imidazólico preferentemente no sustituido en su carbono en posición 2. - an imidazole heterocycle preferably unsubstituted in its carbon in position 2.
- un grupo R que puede ser un grupo alquílico, arílico o alquilarílico, conteniendo entre 1 y 20 átomos de carbono, y puede estar sustituido por grupos sin protones activos como halógeno, sulfonato, carboxilato, éter, tioéter, cetona, sulfóxido, éster, amida, nitrilo. - an R group which can be an alkyl, aryl or alkylaryl group, containing between 1 and 20 carbon atoms, and can be substituted by groups without active protons such as halogen, sulphonate, carboxylate, ether, thioether, ketone, sulfoxide, ester, Amide, nitrile.
- un anión X" que preferentemente puede ser un halogenuro. - an anion X " which preferably can be a halide.
- un espaciador entre el grupo protector de la amina y el heterociclo que queda definido por una longitud de cadena de n eslabones que puede estar comprendida entre 1 y 4 carbonos. - a spacer between the protective group of the amine and the heterocycle that is defined by a chain length of n links that can be comprised between 1 and 4 carbons.
Compuesto según la reivindicación 1 , caracterizado porque el grupo R es también una alquilamina primaria protegida en forma de grupo ftalimido. Compound according to claim 1, characterized in that the R group is also a protected primary alkylamine in the form of a phthalimido group.
Compuesto según la reivindicación 1 , caracterizado porque está seleccionado entre: Compound according to claim 1, characterized in that it is selected from:
- compuesto que reúne los descriptores R = metilo, X" = Br~ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (1.1 , descrito). - compound meets the descriptors R = methyl, X "= Br ~ n = 2 with the imidazole ring unsubstituted in their carbon (1.1, described).
- compuesto que reúne los descriptores R = mesitilo, X" = Br~ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (1.2, descrito). - compound that combines the descriptors R = mesityl, X " = Br ~ and n = 2 with the imidazole ring unsubstituted in their carbons (1.2, described).
- compuesto que reúne los descriptores R = 2,6-diisopropilfenilo, X" = Br~ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (1.3, descrito).
- compound that combines the descriptors R = 2,6-diisopropylphenyl, X " = Br ~ and n = 2 with the imidazole ring unsubstituted in their carbons (1.3, described).
4. Compuesto según reivindicación 1 , de fórmula 2(Si), caracterizado porque tiene en su estructura un grupo trimetoxisililo o trietoxisililo en lugar del grupo ftalimido, 4. Compound according to claim 1, of formula 2 (Si), characterized in that it has in its structure a trimethoxysilyl or triethoxysilyl group instead of the phthalimido group,
(R'0)3Si^N^N. R (R'0) 3 Yes ^ N ^ N. R
X" X "
2(Si) 2 (Yes)
Compuesto según la reivindicación 4, caracterizado porque el grupo R es también una cadena con un grupo trimetoxisililo o trietoxisililo terminal. Compound according to claim 4, characterized in that the R group is also a chain with a trimethoxysilyl or terminal triethoxysilyl group.
Compuesto según la reivindicación 4, caracterizado porque está seleccionado entre: Compound according to claim 4, characterized in that it is selected from:
- compuesto que reúne los descriptores R = metilo, R'O = etóxido, X" = Br" y n = 3 con el anillo imidazólico no sustituido en sus carbonos (2(Si)1 , descrito).- compound that meets the descriptors R = methyl, R'O = ethoxide, X " = Br " and n = 3 with the imidazole ring unsubstituted in its carbons (2 (Si) 1, described).
- compuesto que reúne los descriptores R = mesitilo, R'O = etóxido, X" = Br" y n = 3 con el anillo imidazólico no sustituido en sus carbonos (2(Si)2, descrito).- compound that meets the descriptors R = mesityl, R'O = ethoxide, X " = Br " and n = 3 with the imidazole ring unsubstituted in its carbons (2 (Si) 2, described).
- compuesto que reúne los descriptores R = 2,6-diisopropilfenilo, R'O = etóxido, X" = Br" y n = 3 con el anillo imidazólico no sustituido en sus carbonos (2(Si)3, descrito). - compound that combines the descriptors R = 2,6-diisopropylphenyl, R'O = ethoxide, X " = Br " and n = 3 with the imidazole ring unsubstituted in its carbons (2 (Si) 3, described).
Compuesto según reivindicación 1 , pero de fórmula 2(A), caracterizado porque tiene en su estructura un grupo amina primaria en lugar del grupo ftalimido,
Compound according to claim 1, but of formula 2 (A), characterized in that it has in its structure a primary amine group instead of the phthalimido group,
2(A) 2 (A)
8. Compuesto según la reivindicación 7, caracterizado porque el grupo R es también un cadena con un grupo amina primaria. 8. A compound according to claim 7, characterized in that the R group is also a chain with a primary amine group.
9. Compuesto según la reivindicación 7, caracterizado porque está seleccionado entre: 9. Compound according to claim 7, characterized in that it is selected from:
- compuesto que reúne los descriptores R = metilo, X" = Br" y n = 2 con el anillo imidazólico no sustituido en sus carbonos (2(A)1 , descrito). - compound that combines the descriptors R = methyl, X " = Br " and n = 2 with the imidazole ring unsubstituted in their carbons (2 (A) 1, described).
- compuesto que reúne los descriptores R = mesitilo, X" = Br" y n = 2 con el anillo
imidazólico no sustituido en sus carbonos (2(A)2, descrito). - compound that gathers the descriptors R = mesityl, X " = Br " and n = 2 with the ring imidazole unsubstituted in its carbons (2 (A) 2, described).
- compuesto que reúne los descriptores R = 2,6-diisopropilfenilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (2(A)3, descrito). 10. Un procedimiento de síntesis de los compuestos con fórmula 2(A), definida en la reivindicación 7, caracterizado porque un grupo ftalimido se transforma en una amina primaria en presencia de hidracina, o mediante hidrólisis ácida o básica. - compound that combines the descriptors R = 2,6-diisopropylphenyl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (2 (A) 3, described). 10. A method of synthesis of the compounds with Formula 2 (A), defined in claim 7, characterized in that a phthalimido group is transformed into a primary amine in the presence of hydrazine, or by acidic or basic hydrolysis.
1 1. Complejo de paladio de fórmula l(Si) caracterizado porque tiene una estructura con un ligando carbeno N-heterocíclico (NHC) derivado de compuestos de fórmula1 1. Palladium complex of formula l (Si) characterized in that it has a structure with an N-heterocyclic carbine ligand (NHC) derived from compounds of formula
2(Si), definida en las reivindicaciones 4 y 5, un ligando monodentado U neutro y ligandos aniónicos X, 2 (Si), defined in claims 4 and 5, a neutral U monodentate ligand and anionic ligands X,
l(Si) que comprende: l (Yes) comprising:
- un NHC, derivado de compuestos de la fórmula indicada, preferentemente coordinado por su carbono en posición 2. - an NHC, derived from compounds of the indicated formula, preferably coordinated by its carbon in position 2.
- ligandos X que pueden independientemente ser un haluro, carboxilato, hidruro, o un alquilo, alilo, arilo, alquilarilo, alcóxido, arilóxido, beta-dicetonato, tiolato sustituidos o no sustituidos - X ligands that can independently be a halide, carboxylate, hydride, or an alkyl, allyl, aryl, alkylaryl, alkoxide, aryloxide, beta-diketonate, substituted or unsubstituted thiolate
- un U que es un ligando monodentado neutro con nitrógeno dador, preferentemente una piridina que puede estar sustituida por alquilos o haluros en cualquiera de sus carbonos - a U which is a neutral monodentate ligand with donor nitrogen, preferably a pyridine which may be substituted by alkyls or halides in any of its carbons
12. Complejo según la reivindicación 11 , caracterizado porque está seleccionado entre: 12. Complex according to claim 11, characterized in that it is selected from:
- complejo que reúne los descriptores R = metilo, R'O = etóxido, X" = Γ, n = 3 y U = 4-picolina con el anillo imidazólico no sustituido en sus carbonos (l(Si)1 , descrito). - complex that meets the descriptors R = methyl, R'O = ethoxide, X " = Γ, n = 3 and U = 4-picoline with the imidazole ring unsubstituted in their carbons (1 (Si) 1, described).
- complejo que reúne los descriptores R = mesitilo, R'O = etóxido, X" = Γ, n = 3 y U = 4-picolina con el anillo imidazólico no sustituido en sus carbonos (l(Si)2,
descrito). - complex that combines the descriptors R = mesityl, R'O = ethoxide, X " = Γ, n = 3 and U = 4-picoline with the imidazole ring unsubstituted in their carbons (l (Si) 2, described).
- complejo que reúne los descriptores R = 2,6-diisopropilfenilo, R'O = etóxido, X" = Γ, n = 3 y L' = 4-picolina con el anillo imidazólico no sustituido en sus carbonos (l(Si)3, descrito). - complex that combines the descriptors R = 2,6-diisopropylphenyl, R'O = ethoxide, X " = Γ, n = 3 and L '= 4-picoline with the imidazole ring unsubstituted in their carbons (l (Si) 3 , described).
13. Complejo según la reivindicación 1 1 , con fórmula l(A), caracterizado porque tiene una estructura con un ligando NHC derivado de compuestos de fórmula 2(A), definida en las reivindicaciones 7 y 8. 13. Complex according to claim 1, with formula I (A), characterized in that it has a structure with an NHC ligand derived from compounds of formula 2 (A), defined in claims 7 and 8.
X-Pd-X X-Pd-X
I I
L' L '
l(A) the)
14. Complejo de plata de fórmula 3(Si) caracterizado porque tiene una estructura con un ligando NHC derivado de compuestos de fórmula 2(Si), definida en las reivindicaciones 4 y 5, f=\ 14. Silver complex of formula 3 (Si) characterized in that it has a structure with an NHC ligand derived from compounds of formula 2 (Si), defined in claims 4 and 5, f = \
(R'0)3S¡^ N^ . (R'0) 3 S¡ ^ N ^.
AgX AgX
3(S¡) que comprende: 3 (S¡) comprising:
- un NHC, derivado de compuestos de la fórmula indicada, preferentemente coordinado por su carbono en posición 2. - an NHC, derived from compounds of the indicated formula, preferably coordinated by its carbon in position 2.
15. Complejo según la reivindicación 14, caracterizado porque está seleccionado entre: 15. Complex according to claim 14, characterized in that it is selected from:
- complejo que reúne los descriptores R = metilo, R'O = etóxido, X" = Br~ y n = 3 con el anillo imidazólico no sustituido en sus carbonos (3(Si)1 , descrito). - complex that meets the descriptors R = methyl, R'O = ethoxide, X " = Br ~ and n = 3 with the imidazole ring unsubstituted in their carbons (3 (Si) 1, described).
- complejo que reúne los descriptores R = mesitilo, R'O = etóxido, X" = Br~ y n = 3 con el anillo imidazólico no sustituido en sus carbonos (3(Si)2, descrito).- complex that combines the descriptors R = mesityl, R'O = ethoxide, X " = Br ~ yn = 3 with the imidazole ring unsubstituted in its carbons (3 (Si) 2, described).
- complejo que reúne los descriptores R = 2,6-diisopropilfenilo, R'O = etóxido, X" = Br" y n = 3 con el anillo imidazólico no sustituido en sus carbonos (3(Si)3,
descrito). - complex that combines the descriptors R = 2,6-diisopropylphenyl, R'O = ethoxide, X " = Br " and n = 3 with the imidazole ring unsubstituted in their carbons (3 (Si) 3, described).
16. Complejo de plata según la reivindicación 14 y de fórmula 3(A), caracterizado porque tiene una estructura con un ligando NHC derivado de compuestos de fórmula 2(A), definida en las reivindicaciones 7 y 8. 16. Silver complex according to claim 14 and of formula 3 (A), characterized in that it has a structure with an NHC ligand derived from compounds of formula 2 (A), defined in claims 7 and 8.
3(A) 3 (A)
17. Complejo según la reivindicación 16, caracterizado porque está seleccionado entre: 17. Complex according to claim 16, characterized in that it is selected from:
- complejo que reúne los descriptores R = metilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (3(A)1 , descrito). - complex that combines the descriptors R = methyl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (3 (A) 1, described).
- complejo que reúne los descriptores R = mesitilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (3(A)2, descrito). - complex that combines the descriptors R = mesityl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (3 (A) 2, described).
- complejo que reúne los descriptores R = 2,6-diisopropilfenilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (3(A)3, descrito). - complex that combines the descriptors R = 2,6-diisopropylphenyl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (3 (A) 3, described).
18. Complejo de paladio de fórmula ll(Si) caracterizado porque tiene una estructura con dos ligandos NHC y dos ligandos X como los de los complejos mono(NHC) de paladio de la reivindicación 1 1. 18. Palladium complex of formula ll (Si) characterized in that it has a structure with two NHC ligands and two X ligands like those of the palladium mono (NHC) complexes of claim 1.
ll(Si) ll (Yes)
19. Complejo según la reivindicación 18, caracterizado porque está seleccionado entre: 19. Complex according to claim 18, characterized in that it is selected from:
- complejo que reúne los descriptores R = metilo, R'O = etóxido, X" = ΒΓ y n = 3 con el anillo imidazólico no sustituido en sus carbonos (ll(Si)1 , descrito).
- complejo que reúne los descriptores R = mesitilo, R'O = etóxido, X" = ΒΓ y n = 3 con el anillo imidazólico no sustituido en sus carbonos (ll(Si)2, descrito).- complex that meets the descriptors R = methyl, R'O = ethoxide, X " = ΒΓ and n = 3 with the imidazole ring unsubstituted in their carbons (ll (Si) 1, described). - complex that combines the descriptors R = mesityl, R'O = ethoxide, X " = ΒΓ and n = 3 with the imidazole ring unsubstituted in its carbons (ll (Si) 2, described).
- complejo que reúne los descriptores R = 2,6-diisopropilfenilo, R'O = etóxido, X" = ΒΓ y n = 3 con el anillo imidazólico no sustituido en sus carbonos (ll(Si)3, descrito). - complex that combines the descriptors R = 2,6-diisopropylphenyl, R'O = ethoxide, X " = ΒΓ and n = 3 with the imidazole ring unsubstituted in their carbons (ll (Si) 3, described).
20. Un procedimiento de síntesis de los compuestos con fórmula ll(Si), definida en la reivindicación 18, que comprende: 20. A method of synthesizing the compounds with formula ll (Si), defined in claim 18, comprising:
- la formación, aislamiento y purificación de los complejos de plata de fórmula 2(Si), definida en la reivindicación 14, - the formation, isolation and purification of the silver complexes of formula 2 (Si), defined in claim 14,
- el uso de los anteriores como agentes de transferencia del ligando NHC a precursores de paladio(n) con ligandos lábiles de fórmula general [PdX2L"2] (L"2 = etilendiamina, Ν,Ν,Ν'Ν'-tetrametiletilendiamina, 1 ,5-ciclooctadieno; o L" = benzonitrilo, acetonitrilo). - the use of the above as transfer agents of the NHC ligand to palladium (n) precursors with labile ligands of the general formula [PdX 2 L " 2 ] (L" 2 = ethylenediamine, Ν, Ν, Ν'Ν'-tetramethylethylenediamine , 1,5-cyclooctadiene; or L "= benzonitrile, acetonitrile).
21. Complejo de paladio de fórmula ll(A) caracterizado porque tiene una estructura con dos ligandos NHC y dos ligandos X como los de los complejos mono(NHC) de paladio de la reivindicación 13. 21. Palladium complex of formula ll (A) characterized in that it has a structure with two NHC ligands and two X ligands like those of the palladium mono (NHC) complexes of claim 13.
NH2 NH 2
ll(A) ll (A)
22. Complejo según la reivindicación 21 , caracterizado porque está seleccionado entre: 22. Complex according to claim 21, characterized in that it is selected from:
- complejo que reúne los descriptores R = metilo, X" = Br~ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (ll(A)1 , descrito). - complex that combines the descriptors R = methyl, X " = Br ~ and n = 2 with the imidazole ring unsubstituted in their carbons (ll (A) 1, described).
- complejo que reúne los descriptores R = mesitilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (ll(A)2, descrito). - complex that combines the descriptors R = mesityl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (ll (A) 2, described).
- complejo que reúne los descriptores R = 2,6-diisopropilfenilo, X" = ΒΓ y n = 2 con el anillo imidazólico no sustituido en sus carbonos (ll(A)3, descrito). - complex that combines the descriptors R = 2,6-diisopropylphenyl, X " = ΒΓ and n = 2 with the imidazole ring unsubstituted in their carbons (ll (A) 3, described).
23. Un procedimiento de síntesis de los compuestos con fórmula ll(Si), definida en la
reivindicación 21 , que comprende: 23. A method of synthesis of compounds with formula ll (Si), defined in the claim 21, comprising:
- la formación, aislamiento y purificación de los complejos de plata de fórmula 2(A), definida en la reivindicación 16. - the formation, isolation and purification of the silver complexes of formula 2 (A), defined in claim 16.
- el uso de los anteriores como agentes de transferencia del ligando NHC a precursores de paladio(n) con ligandos lábiles de fórmula general [PdX2L"2] (L"2 = etilendiamina, Ν,Ν,Ν'Ν'-tetrametiletilendiamina, 1 ,5-ciclooctadieno; o L" = benzonitrilo, acetonitrilo). - the use of the above as transfer agents of the NHC ligand to palladium (n) precursors with labile ligands of the general formula [PdX 2 L " 2 ] (L" 2 = ethylenediamine, Ν, Ν, Ν'Ν'-tetramethylethylenediamine , 1,5-cyclooctadiene; or L "= benzonitrile, acetonitrile).
- la transformación en la sales de amonio, [ll(A)1]2+, por tratamiento con un exceso de NH4CI, para posibilitar su caracterización en disolución por RMN. - the transformation into the ammonium salts, [ll (A) 1] 2+ , by treatment with an excess of NH 4 CI, to enable its characterization in NMR solution.
24. Compuesto según reivindicación 1 , de fórmula 4, caracterizado porque tiene una estructura de sal de bisimidazolio en la que el grupo R es una cadena alquílica que actúa de puente entre los dos heterociclos y que queda definida por una longitud de cadena de n' eslabones que puede estar comprendida entre 1 y 3 carbonos. 24. Compound according to claim 1, of formula 4, characterized in that it has a bisimidazolium salt structure in which the group R is an alkyl chain that acts as a bridge between the two heterocycles and is defined by a chain length of n ' links that can be between 1 and 3 carbons.
4 4
25. Compuesto según la reivindicación 24, caracterizado porque tienen un grupo R, definido en la reivindicación 1 , en lugar de una de las cadenas con el grupo ftalimido. 25. Compound according to claim 24, characterized in that they have an R group, defined in claim 1, instead of one of the chains with the phthalimido group.
26. Compuesto según la reivindicación 24, caracterizado porque está seleccionado entre: 26. Compound according to claim 24, characterized in that it is selected from:
- compuesto que reúne los descriptores X" = Br~ n = 2 y n' = 1 con los anillos imidazólico no sustituidos en sus carbonos (4.1 , descrito). - compound that combines the descriptors X " = Br ~ n = 2 and n '= 1 with the imidazole rings unsubstituted in their carbons (4.1, described).
27. Complejo de paladio de fórmula 5 caracterizado porque tiene una estructura con un ligando bis(NHC) derivado de compuestos de fórmula 4, definida en las reivindicaciones 24 y 25, y dos ligandos X como los de los complejos mono(NHC) de paladio de la reivindicación 13,
que comprende: 27. Palladium complex of formula 5 characterized in that it has a structure with a bis (NHC) ligand derived from compounds of formula 4, defined in claims 24 and 25, and two X ligands such as those of the palladium mono (NHC) complexes of claim 13, which includes:
- un bis(NHC), derivado de compuestos de la fórmula 4 indicada, preferentemente coordinados por sus carbonos en posición 2. - a bis (NHC), derived from compounds of the formula 4 indicated, preferably coordinated by their carbons in position 2.
28. Complejo según la reivindicación 27, caracterizado porque está seleccionado entre: 28. Complex according to claim 27, characterized in that it is selected from:
- complejo que reúne los descriptores X" = ΒΓ, n = 2 y n' = 1 con los anillos imidazólico no sustituidos en sus carbonos (5.1 , descrito). - complex that combines the descriptors X " = ΒΓ, n = 2 and n '= 1 with the imidazole rings unsubstituted in their carbons (5.1, described).
29. Complejo según la reivindicación 27, pero de fórmula lll(A), caracterizado porque tiene una estructura con grupos amina primaria en lugar de grupos ftalimido. 29. Complex according to claim 27, but of formula lll (A), characterized in that it has a structure with primary amine groups instead of phthalimido groups.
30. Complejo según la reivindicación 29, caracterizado porque tienen un grupo R, definido en la reivindicación 1 , en lugar de una de las cadenas con el grupo amina. 30. Complex according to claim 29, characterized in that they have an R group, defined in claim 1, instead of one of the chains with the amine group.
31. Complejo según la reivindicación 29, caracterizado porque está seleccionado entre: 31. Complex according to claim 29, characterized in that it is selected from:
- complejo que reúne los descriptores X" = ΒΓ, n = 2 y n' = 1 con los anillos imidazólico no sustituidos en sus carbonos (lll(A)1 , descrito). - complex that brings together the descriptors X " = ΒΓ, n = 2 and n '= 1 with the unsubstituted imidazole rings in their carbons (lll (A) 1, described).
32. Un procedimiento de síntesis de los compuestos con fórmula lll(A), definida en la reivindicación 29, que comprende:
- la formación, aislamiento y purificación de los compuestos de fórmula 4, definida en las reivindicaciones 24 y 25. 32. A method of synthesizing compounds with formula lll (A), defined in claim 29, comprising: - the formation, isolation and purification of the compounds of formula 4, defined in claims 24 and 25.
- la metalación de los anteriores con acetato de paladio para formar y aislar complejos bis(NHC) quelato 5 de la reivindicación 27. - the metallation of the foregoing with palladium acetate to form and isolate bis (NHC) chelate complexes of claim 27.
- desprotección de las aminas primarias mediante tratamiento de los complejos 5 con hidracina. - deprotection of primary amines by treatment of complexes 5 with hydrazine.
33. Compuesto según reivindicación 24, pero de fórmula 6, caracterizado porque tiene una estructura con grupos trimetoxisililo o trietoxisililo en lugar del grupo ftalimido, 33. Compound according to claim 24, but of formula 6, characterized in that it has a structure with trimethoxysilyl or triethoxysilyl groups instead of the phthalimido group,
34. Compuesto según reivindicación 33, caracterizado porque tienen un grupo R, definido en la reivindicación 1 , en lugar de una de las cadenas con el grupo trimetoxisililo o trietoxisililo. 34. Compound according to claim 33, characterized in that they have an R group, defined in claim 1, instead of one of the chains with the trimethoxysilyl or triethoxysilyl group.
35. Complejo de paladio según reivindicación 27, pero de fórmula lll(Si), caracterizado porque tiene una estructura con grupos trimetoxisililo o trietoxisililo en lugar del grupo ftalimido, 35. Palladium complex according to claim 27, but of formula lll (Si), characterized in that it has a structure with trimethoxysilyl or triethoxysilyl groups instead of the phthalimido group,
(RO)3Si^)n χ' χχ ¾Si(OR')3 lll(Si) (RO) 3 Yes ^) n χ ' χ χ ¾Yes (OR') 3 lll (Yes)
36. Complejo de paladio según reivindicación 34, caracterizado porque tienen un grupo R, definido en la reivindicación 1 , en lugar de una de las cadenas con el grupo trimetoxisililo o trietoxisililo.
36. Palladium complex according to claim 34, characterized in that they have an R group, defined in claim 1, instead of one of the chains with the trimethoxysilyl or triethoxysilyl group.
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Non-Patent Citations (4)
| Title |
|---|
| G BORJA ET AL.: "Recyclable hybrid silica-based catalysts derived from Pd-NHC complexes for Suzuki, Heck and Sonogashira reactions", EUROPEAN JOURNAL ORGANIC CHEMISTRY, 2012, pages 3625 - 3635, XP055249321 * |
| H M J WANG ET AL.: "Facile synthesis of silver(I)-carbene complexes. Useful carbene transfer agents", ORGANOMETALLICS, vol. 17, no. 5, 1998, pages 972 - 975., XP055249323 * |
| J R HARJANI ET AL.: "Dalton Transactions", REMOVAL OF METAL IONS FROM AQUEOUS SOLUTIONS USING CHELATING TASK-SPECIFIC IONIC LIQUIDS, 2008, pages 4595 - 4601, XP055249320 * |
| V POLSHETTIWAR ET AL.: "Pd-N-heterocyclic carbene (NHC) organic silica: synthesis and application in carbon-carbon coupling reactions", TETRAHEDRON, vol. 64, 2008, pages 4637 - 4643, XP022607642 * |
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