WO2014071401A1 - Complexes of phosphine ligands comprising a carba-closo-dodecaborate substituent - Google Patents
Complexes of phosphine ligands comprising a carba-closo-dodecaborate substituent Download PDFInfo
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- WO2014071401A1 WO2014071401A1 PCT/US2013/068581 US2013068581W WO2014071401A1 WO 2014071401 A1 WO2014071401 A1 WO 2014071401A1 US 2013068581 W US2013068581 W US 2013068581W WO 2014071401 A1 WO2014071401 A1 WO 2014071401A1
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- Prior art keywords
- group
- alkyl
- complex
- aryl
- alkoxy
- Prior art date
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- 239000003446 ligand Substances 0.000 title claims abstract description 86
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 33
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims description 111
- 125000003118 aryl group Chemical group 0.000 claims description 103
- 125000003545 alkoxy group Chemical group 0.000 claims description 85
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 39
- 229910052736 halogen Inorganic materials 0.000 claims description 30
- 150000002367 halogens Chemical class 0.000 claims description 30
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 28
- 229910052742 iron Inorganic materials 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- 229910052707 ruthenium Inorganic materials 0.000 claims description 26
- 150000001768 cations Chemical class 0.000 claims description 24
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 23
- 229910052741 iridium Inorganic materials 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000000129 anionic group Chemical group 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052703 rhodium Inorganic materials 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 150000001336 alkenes Chemical class 0.000 claims description 16
- 150000001450 anions Chemical group 0.000 claims description 15
- 229910052762 osmium Inorganic materials 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 150000004820 halides Chemical class 0.000 claims description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 238000006880 cross-coupling reaction Methods 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims 9
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- -1 iridium Chemical class 0.000 description 42
- 239000003054 catalyst Substances 0.000 description 40
- 238000005481 NMR spectroscopy Methods 0.000 description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000010931 gold Substances 0.000 description 26
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 23
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 21
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 21
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 19
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 238000005913 hydroamination reaction Methods 0.000 description 16
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 15
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 15
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 15
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 15
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 15
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 11
- 150000001345 alkine derivatives Chemical class 0.000 description 10
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 10
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 9
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 9
- 150000002466 imines Chemical class 0.000 description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 9
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 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 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 6
- 239000004913 cyclooctene Substances 0.000 description 6
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 6
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 6
- 150000003003 phosphines Chemical class 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005865 alkene metathesis reaction Methods 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 3
- 239000004914 cyclooctane Substances 0.000 description 3
- 238000005930 hydroaminomethylation reaction Methods 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- 0 C***1C(*)*CC1 Chemical compound C***1C(*)*CC1 0.000 description 2
- 229910020315 ClAu Inorganic materials 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000004089 sulfido group Chemical group [S-]* 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 1
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- DQQNMIPXXNPGCV-UHFFFAOYSA-N 3-hexyne Chemical compound CCC#CCC DQQNMIPXXNPGCV-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FLCNGVREDYVOMK-UHFFFAOYSA-N NPN1CCCC1 Chemical compound NPN1CCCC1 FLCNGVREDYVOMK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- ZZWABYQKBLDNHJ-UHFFFAOYSA-N [C]=Cc1ccccc1 Chemical class [C]=Cc1ccccc1 ZZWABYQKBLDNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010657 cyclometalation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- COCAUCFPFHUGAA-MGNBDDOMSA-N n-[3-[(1s,7s)-5-amino-4-thia-6-azabicyclo[5.1.0]oct-5-en-7-yl]-4-fluorophenyl]-5-chloropyridine-2-carboxamide Chemical compound C=1C=C(F)C([C@@]23N=C(SCC[C@@H]2C3)N)=CC=1NC(=O)C1=CC=C(Cl)C=N1 COCAUCFPFHUGAA-MGNBDDOMSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000000836 variable-temperature nuclear magnetic resonance spectroscopy Methods 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5004—Acyclic saturated phosphines
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
Definitions
- This invention relates to transition metal catalysts and their use in catalytic reactions such as, but not limited to, olefin polymerization.
- This weak coordinative ability can be enhanced by substitution of some or all of the B-H vertices by alkyl or halo-groups.
- the cluster becomes more reactive towards substitution and oxidation chemistry.
- exhaustive halogenation of the cluster's boron vertices introduces electron withdrawing substituents that enhance the anion's inherent weak coordinative ability and also confers these molecules with inertness to certain chemicals and reactions.
- some perhalogenated carborane counteranions are observed to form isolable salts with potent oxidants such as C 6 o + and CH 3 + .
- the instant application sets forth a composition comprising a transition metal and at least one ligand comprising a carba-closo-dodecaborate substituent.
- the instant application sets forth a ligand having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- A is a cation.
- A may include Li, Na, K, Cs, HN(alkyl)3, or N(alkyl).
- the instant application sets forth a zwitterionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- X 1 is selected from H, alkyl, or aryl.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- the instant application sets forth a zwitterionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected alkyl, aryl, or alkoxy.
- X 1 is of H, alkyl, or aryl.
- Q is a chelating ligand.
- M is a transition metal
- R 1 is H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- X 1 is H, alkyl, or aryl.
- X 2 is an anion selected from H, halide, alkyl, or aryl.
- A is a cation.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- X 1 is selected from H, alkyl, or aryl.
- X 2 is an anion selected from H, halide, alkyl, or aryl.
- Q is a chelating ligand.
- A is a cation.
- M is a transition metal.
- the instant application provides a zwitterionic complex having the following structure:
- R 1 is H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- R 1 is H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- M is a transition metal.
- R 1 is H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- A is a monopositively charged cation or a dipositively charged cation.
- Subscript y is either 1 or 2.
- M is a transition metal.
- the instant application provides a methods of catalyzing chemical reactions, wherein the chemical reactions include, but are not limited to, olefin polymerization, hydroaddition, hydroamination, cross coupling, olefin metathesis hydroformylation, hydrogenation, hydroaminomethylation.
- Figure 1 shows a synthetic procedure for preparing a phosphine ligand containing a carba-closo-dodecaborate ligand substituent in accordance with the present invention.
- Figure 2 shows a solid state structure of an phosphine ligand containing a carba- closo-dodecaborate ligand substituent 2, wherein the hydrogen atoms are omitted for clarity.
- Thermal ellipsoids drawn at the 50% probability level.
- Figure 4 shows non-limiting examples of the types of reactions which the compounds of the instant invention are suitable for catalyzing.
- Figure 5 shows an example of Boron NMR.
- Figure 6 shows a synthetic procedure for preparing a ligand suitable for use in a complex with a transition metal.
- Figure 7 shows X H NMR data for the complex illustrated therein.
- Figure 8 shows 31 P NMR data for the complex illustrated therein.
- Figure 9 shows 13 C NMR data for the complex illustrated therein.
- Figure 10 shows n B NMR data for the complex illustrated therein.
- Figure 1 1 shows a solid state structure of a phosphine complex.
- Figure 12 shows a solid state structure of a phosphine Au complex.
- Figure 13 shows a synthetic procedure for preparing a Au complex.
- Figure 14 shows X H NMR data for the complex illustrated therein.
- Figure 15 shows 31 P NMR data for the complex illustrated therein.
- Figure 16 shows 13 C NMR data for the complex illustrated therein.
- Figure 17 shows n B NMR data for the complex illustrated therein.
- Figure 18 shows example reactions suitable for catalysis by Au complexes.
- Figure 19 shows hydroamination of alkynes results observed using catalysts of the present invention.
- Figure 20 shows hydroamination of alkynes results observed using catalysts of the present invention.
- Figure 21 shows an example of olefin polymerization.
- Figure 22 shows an example of olefin polymerization.
- Figure 23 shows an example of olefin polymerization.
- the present invention provides complexes, such as zwitterionic iridium complex of a phosphine bearing carba-c/osododecaborate anion ligand substituents.
- the present invention also provides methods of making these complexes as well as methods of using these complexes as catalysts.
- the instant compounds and complexes advantageously include ligands with very stable and unreactive 3- dimensionally anionic carborane clusters.
- the instant compounds and complexes are less likely to be made inactive during catalysis compared to standard catalysts that feature ligands with only hydrocarbon substituents.
- zwitterionic or “zwitterion” refers to a neutrally charged compound having both positive and negative charged groups therein.
- halide refers to an anion of F, CI, Br, or I.
- Halogen as used herein includes F, CI, Br, or I.
- alkyl refers to a hydrocarbon group derived from an alkane by removing one hydrogen atom.
- alkyl include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, isopentyl, and n-pentyl.
- Alkyl can include any alkyl group having from about 1 to about 16 carbon atoms.
- alkoxy refers to a group having the formula -O-R, wherein R is alkyl or aryl.
- aryl refers to a substituent derived from an aromatic compound by removing one hydrogen atom. Examples of aryl include, but are not limited to, phenyl, mesityl, 2,6,-diisopropylphenyl, napthyl, and benzyl.
- leaving group refers to group that is displaced by a nucleophile. Examples include, but are not limited to, halides and sulfonate esters, e.g., tosylate.
- chelating refers to a ligand that bonds to a metal center through more than one bond.
- examples include bidentate and tridentate chelating ligands such as, but not limited to, EDTA and citric acid.
- phosphine ligand refers to a ligand that includes a phosphine bond.
- phosphines are derivatives of P3 ⁇ 4 in which one, two or three hydrogens are replaced by, for example, alkyl or aryl substituents. Examples of phosphines include, but are not limited to,
- sil refers to a group having the formula -S1-R3, wherein R is alkyl or aryl.
- carboxystyrene substituent refers to a compound having the following formula -CBUR "1 where the carbon atom is attached to a phosphine ligand as depicted below:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently alkyl, aryl, or alkoxy.
- A is a cation [e.g., Li, Na, K, Cs, HN(alkyl) 3 , or N(alkyl)].
- the present invention further provides compounds and complex, e.g., zwitterionic iridium complex of a phosphine comprising the caxba-closo- dodecaborate anion as a ligand substituent.
- the transition metal e.g., iridium
- the CBnHn " R " group engages in agostic-like bonding, utilizing the B-H bonds adjacent to the carbon atom in the cluster.
- Evidence for the interactions is observed in solution by variable temperature NMR and also in the solid state by a single crystal X-ray diffraction study.
- the instant application provides a composition including a transition metal and at least one ligand that includes at least 1 carba-closo-dodecaborate substituent.
- the instant application provides a ligand having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- A is a cation. In certain embodiments, A is selected from Li, Na, K, Cs, HN(alkyl) 3 , or (alkyl) 4 .
- R 1 is H. In other embodiments R 1 is F. In some other embodiments, R 1 is CI. In other embodiments, R 1 is Br. In certain embodiments,
- R 1 is methyl. In other embodiments, R 1 is ethyl. In some embodiments, R 1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R 1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 1 is octyl. In other embodiments, R 1 is nonyl. In yet others, R 1 is dodecyl.
- R 1 is phenyl, benzyl, or napthyl. In other embodiments R 1 is phenyl. In some other embodiments, R 1 is benzyl. In other embodiments, R 1 is napthyl. In certain embodiments, R 1 is tolulyl. In other embodiments, R 1 is methoxy. In some embodiments, R 1 is ethoxy. In other embodiments R 1 is propoxy. In some other embodiments, R 1 is butoxy. In other embodiments, R 1 is trimethylsilyl. In certain embodiments, R 1 is triethylsilyl.
- R 2 is methyl. In other embodiments, R 2 is ethyl. In some embodiments, R 2 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 2 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R 2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 2 is octyl. In other embodiments, R 2 is nonyl. In yet others, R 2 is dodecyl.
- R 2 is phenyl, benzyl, or napthyl. In other embodiments R 2 is phenyl. In some other embodiments, R 2 is benzyl. In other embodiments, R 2 is napthyl. In certain embodiments, R 2 is tolulyl. In other embodiments, R 2 is methoxy. In some embodiments, R 2 is ethoxy. In other embodiments R 2 is propoxy. In some other embodiments, R 2 is butoxy.
- R 2 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 2 is dimethylamino or diethylamino.
- R 3 is methyl. In other embodiments, R 3 is ethyl. In some embodiments, R 3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 3 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R 3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 3 is octyl. In other embodiments, R 3 is nonyl. In yet others, R 3 is dodecyl.
- R 3 is phenyl, benzyl, or napthyl. In other embodiments R 3 is phenyl. In some other embodiments, R 3 is benzyl. In other embodiments, R 3 is napthyl. In certain embodiments, R 3 is tolulyl. In other embodiments, R 3 is methoxy. In some embodiments, R 3 is ethoxy. In other embodiments R 3 is propoxy. In some other embodiments, R 3 is butoxy.
- R 3 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 3 is dimethylamino or diethylamino.
- the halogen is selected from F, CI, Br, or I.
- the ligand has the following structure:
- the present application provides a zwitterionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- X 1 is selected from H, alkyl, or aryl.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- n is 1. In certain other embodiment set forth herein, n is 2. In some embodiment set forth herein, n is 3. In certain embodiment set forth herein, n is 4. In certain embodiment set forth herein, n is 5. In certain embodiment set forth herein, n is 6.
- M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from Fe, Ru, Co, Ni, or Pd. [0065] In some embodiments of the above formula, R 1 is H. In other embodiments R 1 is F. In some other embodiments, R 1 is CI. In other embodiments, R 1 is Br. In certain embodiments,
- R 1 is methyl. In other embodiments, R 1 is ethyl. In some embodiments, R 1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other
- R 1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 1 is octyl. In other embodiments, R 1 is nonyl. In yet others, R 1 is dodecyl.
- R 1 is phenyl, benzyl, or napthyl. In other embodiments R 1 is phenyl. In some other embodiments, R 1 is benzyl. In other embodiments, R 1 is napthyl. In certain embodiments, R 1 is tolulyl. In other embodiments, R 1 is methoxy. In some embodiments, R 1 is ethoxy. In other embodiments R 1 is propoxy. In some other embodiments, R 1 is butoxy. In other embodiments, R 1 is trimethylsilyl. In certain embodiments, R 1 is triethylsilyl.
- R 2 is methyl. In other embodiments, R 2 is ethyl. In some embodiments, R 2 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 2 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R 2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 2 is octyl. In other embodiments, R 2 is nonyl. In yet others, R 2 is dodecyl.
- R 2 is phenyl, benzyl, or napthyl. In other embodiments R 2 is phenyl. In some other embodiments, R 2 is benzyl. In other embodiments, R 2 is napthyl. In certain embodiments, R 2 is tolulyl. In other embodiments, R 2 is methoxy. In some embodiments, R 2 is ethoxy. In other embodiments R 2 is propoxy. In some other embodiments, R 2 is butoxy.
- R 2 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 2 is dimethylamino or diethylamino.
- R 3 is methyl. In other embodiments, R 3 is ethyl. In some embodiments, R 3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 3 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R 3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 3 is octyl. In other embodiments, R 3 is nonyl. In yet others, R 3 is dodecyl.
- R 3 is phenyl, benzyl, or napthyl. In other embodiments R 3 is phenyl. In some other embodiments, R 3 is benzyl. In other embodiments, R 3 is napthyl. In certain embodiments, R 3 is tolulyl. In other embodiments, R 3 is methoxy. In some embodiments, R 3 is ethoxy. In other embodiments R 3 is propoxy. In some other embodiments, R 3 is butoxy.
- R 3 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 3 is dimethylamino or diethylamino.
- the present application provides a zwitterionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- X 1 is selected from the group consisting of H, alkyl, or aryl.
- Q is a chelating ligand; and M is a transition metal.
- the complex may further comprising 1 to 2 additional Q chelating ligands bonded to M.
- M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- M is selected from Fe, Ru, Co, Ni, or Pd.
- the present application provides an anionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- X 1 is selected from H, alkyl, or aryl.
- X 2 is an anion selected from H, halide, alkyl, or aryl.
- A is a cation.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from the group consisting of Fe, Ru, Co, Ni, or Pd.
- the present application provides an anionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- X 1 is selected from H, alkyl, or aryl.
- X 2 is an anion selected from H, halide, alkyl, or aryl.
- Q is a chelating ligand.
- A is a cation.
- M is a transition metal.
- the complex may further comprise 1 to 2 additional Q ligands bonded to M.
- A is cation.
- A may be selected from Li, Na, K, Cs, FTN(alkyl)3, or N(alkyl) 4 .
- M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- M is selected from the group consisting of Fe, Ru, Co, Ni, or Pd.
- the present application provides a zwitterionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- L is neutral ligand.
- Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6.
- M is a transition metal.
- M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- M is selected from Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- L is CI. In other embodiments, L is
- the present application provides a zwitterionic complex having the following structure:
- R is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R and R are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- M is a transition metal.
- M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- M is selected from Ni, Pd, or Cu. In some of these embodiments, M is in either a +2 or +4 oxidation state.
- the present application provides an anionic complex having the following structure:
- R 1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy.
- R 2 and R 3 are each independently selected from alkyl, aryl, alkoxy, or NR 4 R 5 .
- R 4 and R 5 are each independently selected from alkyl, aryl, or alkoxy.
- A is a monopositively charged cation or a dipositively charged cation.
- Y is 1 or 2.
- M is a transition metal.
- M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
- M is selected from Ni, Pd, or Cu.
- M is in either a +2 or +4 oxidation state.
- the present application provides a complex having the following structure:
- R 1 is H. In other embodiments R 1 is F. In some other embodiments, R 1 is CI. In other embodiments, R 1 is Br. In certain embodiments,
- R 1 is methyl. In other embodiments, R 1 is ethyl. In some embodiments, R 1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other
- R 1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 1 is octyl. In other embodiments, R 1 is nonyl. In yet others, R 1 is dodecyl.
- R 1 is phenyl, benzyl, or napthyl. In other embodiments R 1 is phenyl. In some other embodiments, R 1 is benzyl. In other embodiments, R 1 is napthyl. In certain embodiments, R 1 is tolulyl. In other embodiments, R 1 is methoxy. In some embodiments, R 1 is ethoxy. In other embodiments R 1 is propoxy. In some other embodiments, R 1 is butoxy. In other embodiments, R 1 is trimethylsilyl. In certain embodiments, R 1 is triethylsilyl.
- R 2 is methyl. In other embodiments, R 2 is ethyl. In some embodiments, R 2 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 2 is pentyl (n-pentyl, i- pentyl , cyclopentyl). In other embodiments, R 2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 2 is octyl. In other embodiments, R 2 is nonyl. In yet others, R 2 is dodecyl.
- R 2 is phenyl, benzyl, or napthyl. In other embodiments R 2 is phenyl. In some other embodiments, R 2 is benzyl. In other embodiments, R 2 is napthyl. In certain embodiments, R 2 is tolulyl. In other embodiments, R 2 is methoxy. In some embodiments, R 2 is ethoxy. In other embodiments R 2 is propoxy. In some other embodiments, R 2 is butoxy.
- R 2 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 2 is dimethylamino or
- R 3 is methyl. In other embodiments, R 3 is ethyl. In some embodiments, R 3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R 3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R 3 is pentyl (n-pentyl, i- pentyl , cyclopentyl). In other embodiments, R 3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R 3 is octyl. In other embodiments, R 3 is nonyl. In yet others, R 3 is dodecyl.
- R 3 is phenyl, benzyl, or napthyl. In other embodiments R 3 is phenyl. In some other embodiments, R 3 is benzyl. In other embodiments, R 3 is napthyl. In certain embodiments, R 3 is tolulyl. In other embodiments, R 3 is methoxy. In some embodiments, R 3 is ethoxy. In other embodiments R 3 is propoxy. In some other embodiments, R 3 is butoxy.
- R 3 is NR 4 R 5 , wherein R 4 and R 5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R 3 is dimethylamino or
- L is a neutral ligand selected from
- R 2 and R 3 are isopropyl.
- Certain Preferred Substituents include the following.
- preferred R 1 groups include, but are not limited to carborane H, F, CI, Br, I, benzene, methyl, ethyl, n-propyl, n-butyl, methoxy,eEthoxy, n- propoxy , n-butyloxy, or trimethylsiloxy.
- preferred R 2 groups include benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, or -C 6 F5.
- preferred R 2 groups include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl.
- preferred R 2 groups include methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy.
- preferred R 2 groups include Trimethylsiloxy, triethyl siloxy, or tripropyl siloxy.
- preferred R 4 and R 5 include H.
- R 4 and R 5 independently, include benzene, naphthyl, Mesityl, 2,6- diisopropylphenyl, Tolyl, or -C 6 F5.
- R 4 and R 5 include, independently, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl.
- R 4 and R 5 include trimethylsilyl, triethylsilyl, or tributylsilyl.
- R 2 or R 3 are independently selected from NR 4 R 5 , wherein R 4 and R 5 are H, benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, -C 6 F5, methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, trimethylsilyl, triethylsilyl, or tributylsilyl.
- X 1 and X 2 are independently selected from NR 4 R 5 , wherein NR 4 R 5 is imido.
- R 4 and R 5 are N-Alkyl, NAryl, Sulfido S-R, or Phosphido P-R.
- preferred R 3 groups include benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, or -C 6 F5.
- preferred R 3 groups include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl.
- preferred R 3 groups include methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy.
- preferred R 3 groups include Trimethylsiloxy, triethyl siloxy, or tripropyl siloxy.
- L is a neutral ligand.
- L is a solvent molecule selected from dimethoxy ethane, dioxane, pyridine, tetrahydrofuran, diethyl ether, benzene, toluene, acetonitrile, methylene chloride, chloroform, dimethyl formamide, or acetone.
- L is a phosphine (PR 3 ) containing three alkyl or aryl groups, A phosphite (P(OR) 3 ), P( R 2 ) 3 , a carbene, N-heterocyclic carbene, an alkylidene carbene, a benzylidene carbene, an olefin, an alkyne, a diene, an enone, a polyene, a sulfide (SR 2 ), an alcohol, a ketone, or an ester.
- PR 3 phosphine
- PR 3 phosphine containing three alkyl or aryl groups
- A is selected firm Li , Na , K , Cs , Mg , Ca , Zn 2+ , NH 4 + , HN(Alkyl) 3 + , HN(Me) 3 + , HN(Ethyl) 3 + ,HN(Butyl) 4 + , HN(Aryl) 3 + , H 2 N(Alkyl) 2 + , H 3 NAlkyl + , H 3 NAryl + , a transition metal cation, a main group cation, an alkaline earth cation, or a polyatomic cation.
- X 1 and X 2 are independently selected from H, F, CI, Br, I. In some preferred embodiments, X 1 and X 2 are independently selected from methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, neopentyl,-CH 2 SiMe 3 , benzyl.
- X 1 and X 2 are independently selected from -C 6 H5, naphthyl, Mesityl, or Tolyl.
- X 1 and X 2 are independently selected from methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy.
- X 1 and X 2 are independently selected from
- Trimethylsiloxy Triethyl siloxy, or tripropyl siloxy.
- X 1 and X 2 are independently selected from NR 4 R 5 , wherein R 4 and R 5 are H, benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, -C 6 F5, methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, trimethylsilyl, triethylsilyl, or tributylsilyl.
- X 1 and X 2 are independently selected from NR 4 R 5 , wherein NR 4 R 5 is imido.
- R 4 and R 5 are N-Alkyl, NAryl, Sulfido S-R, or Phosphido P-R.
- the present invention provides methods of making ligands having the following general formula:
- R 1 is selected from the group consisting of H, halide, alkyl, aryl, silyl, and alkoxy.
- R 2 and R 3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR 4 R 5 .
- R 4 and R 5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy.
- halide includes a member selected from the group consisting of fluoride, chloride, bromide, and iodide.
- a + represents a counter-cation.
- A is selected from the group consisting of Li + , Na + , K + , Cs + , HN(alkyl) 3 + , and N(alkyl) 4 + .
- Other suitable cations may include, but are not limited to a member selected from the group consisting of Be 2+ , Mg 2+ , Ca 2+ , Sr ⁇ , and Ba 2+ .
- the methods of making the ligands used herein include providing a solution of a C-H carba-c/oso-dodecaborate anion, having the following formula, in THF:
- the methods further include treating the anion with 1-3 equivalents of a base, wherein the base is w-BuLi (i.e., n-butyl lithium).
- the base is w-BuLi (i.e., n-butyl lithium).
- the methods then include stirring for about three hours. In some embodiments, the methods further include concentrating the reaction under high vacuum. In some of these embodiments, the methods include washing the resulting residue with dry hexane to prepare a solid. In some embodiments, the methods include dissolving the solid in THF or F-C 6 H 5 and treating it with 1.1 equivalents of the X-P(R 2 )(R 3 ) reagent. In some embodiments, the methods include stirring the reaction until completion. In certain embodiments, completion is determined by P NMR analysis. In some embodiments, the methods include concentrating the mixture to dryness, washing the concentrate with hexane.
- the methods include including the solid residue (i.e., the phosphine ligand) extracted in a solvent, wherein the solvent includes, but is not limited to CHCI 3 , CH2CI2, F-C 6 H5).
- the salt byproducts do not dissolve in the solvent.
- the methods include filtering the mixture and drying the solution to afford the desired phosphine in about 95-100% yield.
- the present invention provides methods illustrated by the following reaction scheme:
- X refers to a leaving group.
- the leaving group is selected from the group consisting of CI, Br, and I.
- the present inventions provides methods of making ligands that include, but are not limited to the following synthesis.
- a solution of the C-H carba- c/oso-dodecaborate anion in THF is treated with 1 -3 equivalents of a base (preferably n- BuLi) and stirred for 3 hours and subsequently concentrated under high vacuum.
- the residue is thoroughly washed with dry hexane and the solid is subsequently dissolved in THF or F- C 6 H5 and treated with 1.1 equivalents of the desired X-P(R 2 )(R 3 ) reagent and the reaction is stirred until completion is determined by 31 P NMR analysis.
- the mixture is subsequently concentrated to dryness, washed with hexane, and the solid residue containing the phosphine ligand extracted with a solvent (e.g. CHC13, CH2CI2, F-C 6 H5) where the salt byproducts do not dissolve.
- a solvent e.g. CHC13, CH2CI2, F-C 6 H5
- the mixture is filtered and the solution is concentrated to dryness to afford the desired phosphine in 95-100% yield.
- the instant application sets forth methods of catalyzing chemical reactions, wherein the methods include contacting a complex, set forth herein, with suitable reagents for the chemical reaction to occur.
- the chemical reaction catalyzed is olefin polymerization. In some other embodiments, the chemical reaction catalyzed is
- the chemical reaction catalyzed is cross coupling. In some other embodiments, the chemical reaction catalyzed is hydrogenation.
- the literature describing Au-based catalysts includes a) H. Schmidbaur, et al, B: J. Chem. Sci. 2011, 66, 329-350; Synthesis (Eds.: A.S.K. Hashmi, F. D. Toste), Wiley-VCH, Weinheim, 2012; A. Gomez-Suarez, et al, Angew. Chem. 2012, 124, 8278-8281; Angew. Chem. Int. Ed. 2012, 51, 8156-8159; C. C. J. Loh, et al, Chem. Eur. J. 2012, 18, 10212- 10225; D. Garayalde, et al, ACS Catal.
- the instant application provides methods of catalyzing olefin polymerization reactions comprising contacting a complex described herein with suitable olefin polymerization reagents.
- the instant application provides methods of catalyzing hydroaddition reactions comprising contacting a complex described herein with suitable hydroaddition reagents.
- the instant application provides methods of catalyzing hydroamination reactions comprising contacting a complex described herein with suitable hydroamination reagents.
- the instant application provides methods of catalyzing cross coupling reactions contacting a complex described herein with suitable cross coupling reagents.
- the instant application provides methods of catalyzing olefin metathesis reactions comprising contacting a complex described herein with suitable olefin metathesis reagents.
- the instant application provides methods of catalyzing hydroformylation reactions comprising contacting a complex described herein with suitable hydroformylation reagents.
- the instant application provides methods of catalyzing hydrogenation reactions comprising contacting a complex described herein with suitable hydrogenation reagents.
- the instant application provides methods of catalyzing hydroaminomethylation reactions comprising contacting a complex described herein with suitable hydroaminomethylation reagents.
- Ligands synthesized by this method include the following examples:
- This catalyst is suitable for use in, for example, olefin polymerization
- This catalyst is suitable for use in, for example, olefin hydrogenation
- This catalyst is suitable for use in, for example, olefin polymerization.
- This catalyst is suitable for use in, for example, olefin polymerization
- This catalyst is suitable for use in, for example, Pd-catalyzed cross-coupling.
- This catalyst is suitable for use in, for example, olefin hydrogenation
- This Example shows a synthesis of a phosphine bearing the CBnClif moiety, (iPr) 2 P(CBiiClii) " Li + .
- This group is advantageous because it is very large and the intermediate steric bulk of the isopropyl groups allow the phosphorus lone pair to be accessible for coordination.
- the trimethyl ammonium salt of anion 1 with 2 (in Figure 1) was treated with equivalents of w-BuLi and subsequent quenched with the dianionic intermediate with ClP(iPr) 2 afforded 2 in 98% yield ( Figure 1).
- Anionic phosphine 2 is very soluble in common polar solvents (CH2CI2, CHCI3, THF), and is not sensitive to oxygen in solution or the solid state.
- the X H NMR of 2 displays two distinct doublets of doublets for the CH 3 isopropyl groups, indicating hindered rotation about the P-iPr bonds.
- the driving force for the anion metathesis is the insolubility of LiCl in F-benzene.
- a single crystal X-ray diffraction study confirms the structure of 3 ( THT If the reaction is performed in THF, a solvent where LiCl is soluble, THT is liberated and an unusual anionic ClAu-Li+ complex 3 (LiCl) is isolated.
- Complex 3 (LiCl) can also be prepared by the treatment of isolated 3(THT) with LiCl in THF. In contrast to 3(THT) it was possible to grow single crystals of 3 (LiCl) without significant disorder and thus examined the solid state structural aspects of this molecule.
- the P-Au bond length is 2.2477(12) A, which is close to a neutral ortho-dicarbaclosodecaborane substituted phosphine AuCl complex (2.232(3) A).
- the chloride ligand (trans from the phosphine) is at a distance of 2.2883(12) A from the metal center.
- the carborane substituent retains a significant amount of weakly coordinating character, even though it is forced into a position close to the metal center.
- This Example demonstrates the catalytic properties of complexes 3 in the hydroamination of primary amines with alkynes.
- This example observed the addition of aniline to phenyl acetylene.
- a 1 : 1 neat mixture of amine and alkyne was added to 0.1 mol% of complex 3 ( ⁇ >, where upon an exothermic reaction occurred.
- Monitoring the reaction by l H NMR revealed the hydroamination was >95% complete in 1 hour (entry 1, Table 1).
- Identical results were obtained with 3(LiCl), (entry 2, Table 1), hence further catalytic tests were carried out using exclusively 3(THT).
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Abstract
This invention relates to complexes comprising phosphine ligands comprising a carbo-closo-dodecaborate substituent and transition metals as well as their use in catalytic reactions.
Description
COMPLEXES OF PHOSPHINE LIGANDS COMPRISING A C ARB A- CLOSO-DODECABORATE SUBSTITUENT
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application Serial Number 61/722,740, filed 5 November 2012, the entire contents of which are herein incorporated by reference in its entirety for all purposes.
FIELD OF THE INVENTION
[0002] This invention relates to transition metal catalysts and their use in catalytic reactions such as, but not limited to, olefin polymerization.
BACKGROUND OF THE INVENTION
[0003] Modern transition metal catalysis is based, in part, on metal complexes that include a diverse range of ligand frameworks, such as bulky R-groups which influence the catalytic activity of these complexes. These types of sterically demanding ligands kinetically protect the active metal center and promote substrate exchange and low coordination, both of which are necessary processes for high turnover numbers (TON). These ligands also influence the metal center's selectivity for product formation and substrate consumption. Of the many ligands used in modern metal catalysis, dicarba-closo-dodecaborane (C2B10) clusters (M. Scholz, et al, Chem. Rev. 2011, 1 1 1, 7035-7062; N. Fey, et al, Organometallics 2012, 31, 2907-2913; A. M. Spokoyny, et al, Nature Chem. 201 1, 3, 590-596; J. I. van der Vlugt, Angew. Chem. 2010, 122, 260-263; Angew. Chem. Int. Ed. 2010, 49, 252-255) are not commonly used. These boron containing ligands have not been employed much in the relevant field because of potential negative side reactions, such as B-H activation and cyclometalation. For these and related reasons, such as intramolecular reactions, the synthetic utility of carborane bearing ligands in the area of catalysis has been limited.
[0004] Complexes that contain ligands functionalized with related carba-closo- dodecaborate anions (CBn ) directly bound to the coordinating atom via the carborane hypercarbon have not been reported (S. K5rbe, et al., Chem. Rev. 2006, 106, 5208-5249). Although similar in size to their neutral dicarba-cousins (C2B10), isoelectronic (CBn-) clusters have significantly different properties. The negative charge of these clusters is delocalized throughout the 12 cage atoms, resulting in a very weakly coordinating anion. This weak coordinative ability can be enhanced by substitution of some or all of the B-H vertices by alkyl or halo-groups. In the case of alkyl substitution, the cluster becomes more
reactive towards substitution and oxidation chemistry. On the other hand, exhaustive halogenation of the cluster's boron vertices introduces electron withdrawing substituents that enhance the anion's inherent weak coordinative ability and also confers these molecules with inertness to certain chemicals and reactions. For example, some perhalogenated carborane counteranions are observed to form isolable salts with potent oxidants such as C6o+ and CH3 +.
[0005] There is currently a need, for example, for single component gold catalysts which offer a number of advantages compared to traditional two component systems that utilize Ag+ or strong Bronsted acid additives. These additives not only increase the cost of the systems, but can also induce side reactions or different reactivity all together. Accordingly, there exists a need in the field to which the instant invention relates regarding the development and use of novel bulky ligands and their associated transition metal complexes. Surprisingly, the instant invention meets these as well as other needs in the relevant field.
BRIEF SUMMARY OF THE INVENTION
[0006] In one embodiment, the instant application sets forth a composition comprising a transition metal and at least one ligand comprising a carba-closo-dodecaborate substituent.
[0007] In a second embodiment, the instant application sets forth a ligand having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. A is a cation. For example, A may include Li, Na, K, Cs, HN(alkyl)3, or N(alkyl).
[0008] In a third embodiment, the instant application sets forth a zwitterionic complex having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. X1 is selected from H, alkyl, or aryl. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal.
[0009] In a fourth embodiment, the instant application sets forth a zwitterionic complex having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected alkyl, aryl, or alkoxy. X1 is of H, alkyl, or aryl. Q is a chelating ligand. M is a transition metal
[0010] In a fifth embodiment, the instant application sets forth an anionic complex having the following structure:
R1 is H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. X1 is H, alkyl, or aryl. X2 is an anion selected from H, halide, alkyl, or aryl. A is a cation. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal.
[0011] In a sixth embodiment, the instant application sets forth an anionic complex having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. X1 is selected from H, alkyl, or aryl. X2 is an anion selected from H, halide, alkyl, or aryl. Q is a chelating ligand. A is a cation. M is a transition metal.
[0012] In a seventh embodiment, the instant application provides a zwitterionic complex having the following structure:
R1 is H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal.
[0013] In an eighth embodiment, the instant application provides a zwitterionic complex having the following structure:
R1 is H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. M is a transition metal.
[0014] In a ninth embodiment, the instant application provides an anionic complex having the following structure:
R1 is H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. A is a monopositively charged cation or a dipositively charged cation. Subscript y is either 1 or 2. M is a transition metal.
[0015] In a tenth embodiment, the instant application provides a methods of catalyzing chemical reactions, wherein the chemical reactions include, but are not limited to, olefin polymerization, hydroaddition, hydroamination, cross coupling, olefin metathesis hydroformylation, hydrogenation, hydroaminomethylation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 shows a synthetic procedure for preparing a phosphine ligand containing a carba-closo-dodecaborate ligand substituent in accordance with the present invention.
[0017] Figure 2 shows a solid state structure of an phosphine ligand containing a carba- closo-dodecaborate ligand substituent 2, wherein the hydrogen atoms are omitted for clarity. Thermal ellipsoids drawn at the 50% probability level.
[0018] Figure 3 shows the synthesis of complexes 3(THT) and 3(LiCl), top left and right respectively. Solid state structure of 3(THT), bottom left. Solid state structure of 3(LiCl), bottom right. Selected bond lengths for 3(LiCl); P-Au = 2.2477(12), P-Cl = 1.943(5), P-C2 = 1.858(6), P-C3 = 1.864(5), Au-Cl = 2.2883(12). Bond lengths in A, thermal ellipsoids drawn at the 50% probability level, hydrogen atoms in both 3(THT) and 3(LiCl) omitted for clarity.
[0019] Figure 4 shows non-limiting examples of the types of reactions which the compounds of the instant invention are suitable for catalyzing.
[0020] Figure 5 shows an example of Boron NMR.
[0021] Figure 6 shows a synthetic procedure for preparing a ligand suitable for use in a complex with a transition metal.
[0022] Figure 7 shows XH NMR data for the complex illustrated therein. [0023] Figure 8 shows 31P NMR data for the complex illustrated therein. [0024] Figure 9 shows 13C NMR data for the complex illustrated therein.
[0025] Figure 10 shows nB NMR data for the complex illustrated therein.
[0026] Figure 1 1 shows a solid state structure of a phosphine complex.
[0027] Figure 12 Figure 2 shows a solid state structure of a phosphine Au complex.
[0028] Figure 13 shows a synthetic procedure for preparing a Au complex.
[0029] Figure 14 shows XH NMR data for the complex illustrated therein.
[0030] Figure 15 shows 31P NMR data for the complex illustrated therein.
[0031] Figure 16 shows 13C NMR data for the complex illustrated therein.
[0032] Figure 17 shows nB NMR data for the complex illustrated therein.
[0033] Figure 18 shows example reactions suitable for catalysis by Au complexes.
[0034] Figure 19 shows hydroamination of alkynes results observed using catalysts of the present invention.
[0035] Figure 20 shows hydroamination of alkynes results observed using catalysts of the present invention.
[0036] Figure 21 shows an example of olefin polymerization.
[0037] Figure 22 shows an example of olefin polymerization.
[0038] Figure 23 shows an example of olefin polymerization.
DETAILED DESCRIPTION OF THE INVENTION GENERAL
[0039] The present invention provides complexes, such as zwitterionic iridium complex of a phosphine bearing carba-c/osododecaborate anion ligand substituents. The present invention also provides methods of making these complexes as well as methods of using these complexes as catalysts.
[0040] Whereas as other catalysts suffer from a variety of disadvantages, the instant compounds and complexes advantageously include ligands with very stable and unreactive 3- dimensionally anionic carborane clusters. The instant compounds and complexes are less likely to be made inactive during catalysis compared to standard catalysts that feature ligands with only hydrocarbon substituents.
DEFINITIONS
[0041] As used herein, the term "zwitterionic" or "zwitterion" refers to a neutrally charged compound having both positive and negative charged groups therein.
[0042] As used herein, the term "halide," refers to an anion of F, CI, Br, or I. "Halogen" as used herein includes F, CI, Br, or I.
[0043] As used herein, the term "alkyl," refers to a hydrocarbon group derived from an alkane by removing one hydrogen atom. Examples of alkyl include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, isopentyl, and n-pentyl. Alkyl can include any alkyl group having from about 1 to about 16 carbon atoms.
[0044] As used herein, the term "alkoxy" refers to a group having the formula -O-R, wherein R is alkyl or aryl.
[0045] As used herein, the term "aryl" refers to a substituent derived from an aromatic compound by removing one hydrogen atom. Examples of aryl include, but are not limited to, phenyl, mesityl, 2,6,-diisopropylphenyl, napthyl, and benzyl.
[0046] As used herein, the term "leaving group," refers to group that is displaced by a nucleophile. Examples include, but are not limited to, halides and sulfonate esters, e.g., tosylate.
[0047] As used herein, chelating refers to a ligand that bonds to a metal center through more than one bond. Examples include bidentate and tridentate chelating ligands such as, but not limited to, EDTA and citric acid.
[0048] As used herein, the term "phosphine ligand," refers to a ligand that includes a phosphine bond. In the relevant field to which the instant invention pertains, phosphines are derivatives of P¾ in which one, two or three hydrogens are replaced by, for example, alkyl or aryl substituents. Examples of phosphines include, but are not limited to,
triphenylphosphine.
[0049] As used herein, the term "silyl" refers to a group having the formula -S1-R3, wherein R is alkyl or aryl.
[0050] As used herein, the term "carba-closo-dodecaborate substituent" refers to a compound having the following formula -CBUR "1 where the carbon atom is attached to a phosphine ligand as depicted below:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently alkyl, aryl, or alkoxy. A is a cation [e.g., Li, Na, K, Cs, HN(alkyl)3, or N(alkyl)].
COMPLEXES
[0051] In certain embodiments, the present invention further provides compounds and complex, e.g., zwitterionic iridium complex of a phosphine comprising the caxba-closo- dodecaborate anion as a ligand substituent. In some embodiments, when the transition metal, e.g., iridium, is bonded directly to a phosphine ligand, the CBnHn" R" group engages in agostic-like bonding, utilizing the B-H bonds adjacent to the carbon atom in the cluster. Evidence for the interactions is observed in solution by variable temperature NMR and also in the solid state by a single crystal X-ray diffraction study. A significant lengthening of a tmns-olefm C-C bond suggests this ligand substituent has a pronounced iraws-influence, which is in contrast to the unfunctionalized weakly coordinating HCBnHn" anion.
[0052] In some embodiments, the instant application provides a composition including a transition metal and at least one ligand that includes at least 1 carba-closo-dodecaborate substituent.
[0053] In certain embodiments, the instant application provides a ligand having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. A is a cation. In certain embodiments, A is selected from Li, Na, K, Cs, HN(alkyl)3, or (alkyl)4.
[0054] In some embodiments of the above formula, R1 is H. In other embodiments R1 is F. In some other embodiments, R1 is CI. In other embodiments, R1 is Br. In certain
embodiments, R1 is methyl. In other embodiments, R1 is ethyl. In some embodiments, R1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R1 is octyl. In other embodiments, R1 is nonyl. In yet others, R1 is dodecyl.
[0055] In some embodiments of the above formula, R1 is phenyl, benzyl, or napthyl. In other embodiments R1 is phenyl. In some other embodiments, R1 is benzyl. In other embodiments, R1 is napthyl. In certain embodiments, R1 is tolulyl. In other embodiments, R1 is methoxy. In some embodiments, R1 is ethoxy. In other embodiments R1 is propoxy. In some other embodiments, R1 is butoxy. In other embodiments, R1 is trimethylsilyl. In certain embodiments, R1 is triethylsilyl.
[0056] In certain embodiments, R2 is methyl. In other embodiments, R2 is ethyl. In some embodiments, R2 is propyl (e.g., n-propyl, i-propyl). In other embodiments R2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R2 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R2 is octyl. In other embodiments, R2 is nonyl. In yet others, R2 is dodecyl.
[0057] In some embodiments of the above formula, R2 is phenyl, benzyl, or napthyl. In other embodiments R2 is phenyl. In some other embodiments, R2 is benzyl. In other embodiments, R2 is napthyl. In certain embodiments, R2 is tolulyl. In other embodiments, R2 is methoxy. In some embodiments, R2 is ethoxy. In other embodiments R2 is propoxy. In some other embodiments, R2 is butoxy. In some embodiments, R2 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R2 is dimethylamino or diethylamino.
[0058] In certain embodiments, R3 is methyl. In other embodiments, R3 is ethyl. In some embodiments, R3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R3 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R3 is octyl. In other embodiments, R3 is nonyl. In yet others, R3 is dodecyl.
[0059] In some embodiments of the above formula, R3 is phenyl, benzyl, or napthyl. In other embodiments R3 is phenyl. In some other embodiments, R3 is benzyl. In other embodiments, R3 is napthyl. In certain embodiments, R3 is tolulyl. In other embodiments, R3 is methoxy. In some embodiments, R3 is ethoxy. In other embodiments R3 is propoxy. In some other embodiments, R3 is butoxy. In some embodiments, R3 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R3 is dimethylamino or diethylamino.
[0060] In some embodiments, the halogen is selected from F, CI, Br, or I.
[0061] In some embodiments, the ligand has the following structure:
[0062] In some other embodiments, the present application provides a zwitterionic complex having the following structure:
R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. X1 is selected from H, alkyl, or aryl. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal.
[0063] In certain embodiment set forth herein, n is 1. In certain other embodiment set forth herein, n is 2. In some embodiment set forth herein, n is 3. In certain embodiment set forth herein, n is 4. In certain embodiment set forth herein, n is 5. In certain embodiment set forth herein, n is 6.
[0064] In some embodiments, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from Fe, Ru, Co, Ni, or Pd.
[0065] In some embodiments of the above formula, R1 is H. In other embodiments R1 is F. In some other embodiments, R1 is CI. In other embodiments, R1 is Br. In certain
embodiments, R1 is methyl. In other embodiments, R1 is ethyl. In some embodiments, R1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other
embodiments, R1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R1 is octyl. In other embodiments, R1 is nonyl. In yet others, R1 is dodecyl.
[0066] In some embodiments of the above formula, R1 is phenyl, benzyl, or napthyl. In other embodiments R1 is phenyl. In some other embodiments, R1 is benzyl. In other embodiments, R1 is napthyl. In certain embodiments, R1 is tolulyl. In other embodiments, R1 is methoxy. In some embodiments, R1 is ethoxy. In other embodiments R1 is propoxy. In some other embodiments, R1 is butoxy. In other embodiments, R1 is trimethylsilyl. In certain embodiments, R1 is triethylsilyl.
[0067] In certain embodiments, R2 is methyl. In other embodiments, R2 is ethyl. In some embodiments, R2 is propyl (e.g., n-propyl, i-propyl). In other embodiments R2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R2 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R2 is octyl. In other embodiments, R2 is nonyl. In yet others, R2 is dodecyl.
[0068] In some embodiments of the above formula, R2 is phenyl, benzyl, or napthyl. In other embodiments R2 is phenyl. In some other embodiments, R2 is benzyl. In other embodiments, R2 is napthyl. In certain embodiments, R2 is tolulyl. In other embodiments, R2 is methoxy. In some embodiments, R2 is ethoxy. In other embodiments R2 is propoxy. In some other embodiments, R2 is butoxy. In some embodiments, R2 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R2 is dimethylamino or diethylamino.
[0069] In certain embodiments, R3 is methyl. In other embodiments, R3 is ethyl. In some embodiments, R3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R3 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other embodiments, R3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R3 is octyl. In other embodiments, R3 is nonyl. In yet others, R3 is dodecyl.
[0070] In some embodiments of the above formula, R3 is phenyl, benzyl, or napthyl. In other embodiments R3 is phenyl. In some other embodiments, R3 is benzyl. In other embodiments, R3 is napthyl. In certain embodiments, R3 is tolulyl. In other embodiments, R3
is methoxy. In some embodiments, R3 is ethoxy. In other embodiments R3 is propoxy. In some other embodiments, R3 is butoxy. In some embodiments, R3 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R3 is dimethylamino or diethylamino.
[0071] In some embodiments, the present application provides a zwitterionic complex having the following structure:
[0072] R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. X1 is selected from the group consisting of H, alkyl, or aryl. Q is a chelating ligand; and M is a transition metal. The complex may further comprising 1 to 2 additional Q chelating ligands bonded to M. In any embodiment, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In some embodiments, M is selected from Fe, Ru, Co, Ni, or Pd.
[0073] In some embodiments, the present application provides an anionic complex having the following structure:
[0074] R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. X1 is selected from H, alkyl, or aryl. X2 is an anion
selected from H, halide, alkyl, or aryl. A is a cation. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal. In some embodiments, M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from the group consisting of Fe, Ru, Co, Ni, or Pd.
[0075] In some embodiments, the present application provides an anionic complex having the following structure:
[0076] R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. X1 is selected from H, alkyl, or aryl. X2 is an anion selected from H, halide, alkyl, or aryl. Q is a chelating ligand. A is a cation. M is a transition metal. The complex may further comprise 1 to 2 additional Q ligands bonded to M. A is cation. For example, A may be selected from Li, Na, K, Cs, FTN(alkyl)3, or N(alkyl)4. M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. M is selected from the group consisting of Fe, Ru, Co, Ni, or Pd.
[0077] In some embodiments, the present application provides a zwitterionic complex having the following structure:
[0078] R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. L is neutral ligand. Subscript n is an integer selected from 1, 2, 3, 4, 5, or 6. M is a transition metal. In some embodiments, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au.
[0079] In some preferred embodiments, L is CI. In other embodiments, L is
tetrahydrothiophene.
[0080] In some embodiments, the present application provides a zwitterionic complex having the following structure:
[0081] R is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R and R are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. M is a transition metal. In some embodiments, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is
selected from Ni, Pd, or Cu. In some of these embodiments, M is in either a +2 or +4 oxidation state.
[0082] In some embodiments, the present application provides an anionic complex having the following structure:
[0083] R1 is selected from H, halogen, alkyl, aryl, silyl, or alkoxy. R2 and R3 are each independently selected from alkyl, aryl, alkoxy, or NR4R5. R4 and R5 are each independently selected from alkyl, aryl, or alkoxy. A is a monopositively charged cation or a dipositively charged cation. Y is 1 or 2. M is a transition metal. In some embodiments, M is selected from Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, or Au. In other embodiments, M is selected from Ni, Pd, or Cu. In certain embodiments, M is in either a +2 or +4 oxidation state.
[0084] In some embodiments, the present application provides a complex having the following structure:
[0085] In some embodiments of the above formula, R1 is H. In other embodiments R1 is F. In some other embodiments, R1 is CI. In other embodiments, R1 is Br. In certain
embodiments, R1 is methyl. In other embodiments, R1 is ethyl. In some embodiments, R1 is propyl (e.g., n-propyl, i-propyl). In other embodiments R1 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R1 is pentyl (n-pentyl, i-pentyl , cyclopentyl). In other
embodiments, R1 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R1 is octyl. In other embodiments, R1 is nonyl. In yet others, R1 is dodecyl.
[0086] In any of the above embodiments, R1 is phenyl, benzyl, or napthyl. In other embodiments R1 is phenyl. In some other embodiments, R1 is benzyl. In other embodiments, R1 is napthyl. In certain embodiments, R1 is tolulyl. In other embodiments, R1 is methoxy. In some embodiments, R1 is ethoxy. In other embodiments R1 is propoxy. In some other embodiments, R1 is butoxy. In other embodiments, R1 is trimethylsilyl. In certain embodiments, R1 is triethylsilyl.
[0087] In certain of the above embodiments, R2 is methyl. In other embodiments, R2 is ethyl. In some embodiments, R2 is propyl (e.g., n-propyl, i-propyl). In other embodiments
R2 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R2 is pentyl (n-pentyl, i- pentyl , cyclopentyl). In other embodiments, R2 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R2 is octyl. In other embodiments, R2 is nonyl. In yet others, R2 is dodecyl.
[0088] In some of the above embodiments of the above formula, R2 is phenyl, benzyl, or napthyl. In other embodiments R2 is phenyl. In some other embodiments, R2 is benzyl. In other embodiments, R2 is napthyl. In certain embodiments, R2 is tolulyl. In other embodiments, R2 is methoxy. In some embodiments, R2 is ethoxy. In other embodiments R2 is propoxy. In some other embodiments, R2 is butoxy. In some embodiments, R2 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R2 is dimethylamino or
diethylamino.
[0089] In certain of the above embodiments, R3 is methyl. In other embodiments, R3 is ethyl. In some embodiments, R3 is propyl (e.g., n-propyl, i-propyl). In other embodiments R3 is butyl (e.g., n-butyl, i-butyl). In some other embodiments, R3 is pentyl (n-pentyl, i- pentyl , cyclopentyl). In other embodiments, R3 is hexyl (n-hexyl, cyclohexyl). In certain embodiments, R3 is octyl. In other embodiments, R3 is nonyl. In yet others, R3 is dodecyl.
[0090] In some of the above embodiments of the above formula, R3 is phenyl, benzyl, or napthyl. In other embodiments R3 is phenyl. In some other embodiments, R3 is benzyl. In other embodiments, R3 is napthyl. In certain embodiments, R3 is tolulyl. In other embodiments, R3 is methoxy. In some embodiments, R3 is ethoxy. In other embodiments R3 is propoxy. In some other embodiments, R3 is butoxy. In some embodiments, R3 is NR4R5, wherein R4 and R5 are independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. In certain embodiments, R3 is dimethylamino or
diethylamino.
[0091] In some of the above embodiments, L is a neutral ligand selected from
cyclooctadiene.
[0092] In certain preferred embodiments of the above, R2 and R3 are isopropyl. [0093] Certain Preferred Substituents include the following.
[0094] In some of the above embodiments, preferred R1 groups include, but are not limited to carborane H, F, CI, Br, I, benzene, methyl, ethyl, n-propyl, n-butyl, methoxy,eEthoxy, n- propoxy , n-butyloxy, or trimethylsiloxy.
[0095] In some of the above embodiments, preferred R2 groups include benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, or -C6F5. In some of the above embodiments, preferred R2 groups include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl. In some of the above embodiments, preferred R2 groups include methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy. In some of the above embodiments, preferred R2 groups include Trimethylsiloxy, triethyl siloxy, or tripropyl siloxy.
[0096] In some of the above embodiments, preferred R4 and R5 include H. In other preferred embodiments, R4 and R5, independently, include benzene, naphthyl, Mesityl, 2,6- diisopropylphenyl, Tolyl, or -C6F5. In other preferred embodiments, R4 and R5 include, independently, methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl. In other preferred embodiments, R4 and R5 include trimethylsilyl, triethylsilyl, or tributylsilyl.
[0097] In some preferred embodiments, R2 or R3 are independently selected from NR4R5, wherein R4 and R5 are H, benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, -C6F5, methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, trimethylsilyl, triethylsilyl, or tributylsilyl.
[0098] In some preferred embodiments, X1 and X2 are independently selected from NR4R5, wherein NR4R5 is imido. In some embodiments, R4 and R5 are N-Alkyl, NAryl, Sulfido S-R, or Phosphido P-R.
[0099] In some of the above embodiments, preferred R3 groups include benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, or -C6F5. In some of the above embodiments, preferred R3 groups include methyl, ethyl, propyl, butyl, isopropyl, t-butyl, adamantly, cyclohexyl, or cyclopentyl. In some of the above embodiments, preferred R3 groups include methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy. In some of the above embodiments, preferred R3 groups include Trimethylsiloxy, triethyl siloxy, or tripropyl siloxy.
[0100] In other preferred embodiments, L is a neutral ligand. In some embodiments, L is a solvent molecule selected from dimethoxy ethane, dioxane, pyridine, tetrahydrofuran, diethyl ether, benzene, toluene, acetonitrile, methylene chloride, chloroform, dimethyl formamide, or acetone. In other preferred embodiments, L is a phosphine (PR3) containing three alkyl or aryl groups, A phosphite (P(OR)3), P( R2)3, a carbene, N-heterocyclic carbene, an alkylidene
carbene, a benzylidene carbene, an olefin, an alkyne, a diene, an enone, a polyene, a sulfide (SR2), an alcohol, a ketone, or an ester.
I _|_ _|_ _|_ 2"!" 2 I
[0101] In some preferred embodiments, A is selected firm Li , Na , K , Cs , Mg , Ca , Zn2+, NH4 +, HN(Alkyl)3 +, HN(Me)3 + , HN(Ethyl)3 +,HN(Butyl)4 +, HN(Aryl)3 +, H2N(Alkyl)2 +, H3NAlkyl+, H3NAryl+, a transition metal cation, a main group cation, an alkaline earth cation, or a polyatomic cation.
[0102] In some preferred embodiments, X1 and X2 are independently selected from H, F, CI, Br, I. In some preferred embodiments, X1 and X2 are independently selected from methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, neopentyl,-CH2SiMe3, benzyl.
[0103] In some preferred embodiments, X1 and X2 are independently selected from -C6H5, naphthyl, Mesityl, or Tolyl.
[0104] In some preferred embodiments, X1 and X2 are independently selected from methoxy, ethoxy, propoxy , butyloxy, isopropoxy, t-butoxy, phenoxy, or mesityloxy.
[0105] In some preferred embodiments, X1 and X2 are independently selected from
Trimethylsiloxy, triethyl siloxy, or tripropyl siloxy).
[0106] In some preferred embodiments, X1 and X2 are independently selected from NR4R5, wherein R4 and R5 are H, benzene, naphthyl, Mesityl, 2,6-diisopropylphenyl, Tolyl, -C6F5, methyl, ethyl, propyl, butyl, isopropyl, t-Butyl, adamantly, cyclohexyl, cyclopentyl, trimethylsilyl, triethylsilyl, or tributylsilyl.
[0107] In some preferred embodiments, X1 and X2 are independently selected from NR4R5, wherein NR4R5 is imido. In some embodiments, R4 and R5 are N-Alkyl, NAryl, Sulfido S-R, or Phosphido P-R.
METHOD OF MAKING COMPOUNDS AND COMPLEXES
[0108] In some embodiments, the present invention provides methods of making ligands having the following general formula:
In these embodiments, R1 is selected from the group consisting of H, halide, alkyl, aryl, silyl, and alkoxy. R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5. In these embodiments, R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy. In any embodiment set forth herein, halide includes a member selected from the group consisting of fluoride, chloride, bromide, and iodide. A+ represents a counter-cation. In some embodiments, A is selected from the group consisting of Li+, Na+, K+, Cs+, HN(alkyl)3 +, and N(alkyl)4 +. Other suitable cations may include, but are not limited to a member selected from the group consisting of Be2+, Mg2+, Ca2+, Sr^, and Ba2+.
[0109] In some embodiments, the methods of making the ligands used herein include providing a solution of a C-H carba-c/oso-dodecaborate anion, having the following formula, in THF:
[0110] In certain embodiments, the methods further include treating the anion with 1-3 equivalents of a base, wherein the base is w-BuLi (i.e., n-butyl lithium). In some
embodiments, the methods then include stirring for about three hours. In some embodiments, the methods further include concentrating the reaction under high vacuum. In some of these embodiments, the methods include washing the resulting residue with dry hexane to prepare a solid. In some embodiments, the methods include dissolving the solid in THF or F-C6H5 and treating it with 1.1 equivalents of the X-P(R2)(R3) reagent. In some embodiments, the methods include stirring the reaction until completion. In certain embodiments, completion is
determined by P NMR analysis. In some embodiments, the methods include concentrating the mixture to dryness, washing the concentrate with hexane. In some embodiments, the methods include including the solid residue ( i.e., the phosphine ligand) extracted in a solvent, wherein the solvent includes, but is not limited to CHCI3, CH2CI2, F-C6H5). In some of these embodiments, the salt byproducts do not dissolve in the solvent. In some embodiments, the methods include filtering the mixture and drying the solution to afford the desired phosphine in about 95-100% yield.
[0111] In some embodiments, the present invention provides methods illustrated by the following reaction scheme:
[0112] In any of the embodiments set forth herein, X refers to a leaving group. In some of these embodiments, the leaving group is selected from the group consisting of CI, Br, and I.
[0113] In some embodiments, the present inventions provides methods of making ligands that include, but are not limited to the following synthesis. A solution of the C-H carba- c/oso-dodecaborate anion in THF is treated with 1 -3 equivalents of a base (preferably n- BuLi) and stirred for 3 hours and subsequently concentrated under high vacuum. The residue is thoroughly washed with dry hexane and the solid is subsequently dissolved in THF or F- C6H5 and treated with 1.1 equivalents of the desired X-P(R2)(R3) reagent and the reaction is stirred until completion is determined by 31P NMR analysis. The mixture is subsequently concentrated to dryness, washed with hexane, and the solid residue containing the phosphine ligand extracted with a solvent ( e.g. CHC13, CH2CI2, F-C6H5) where the salt byproducts do not dissolve. The mixture is filtered and the solution is concentrated to dryness to afford the desired phosphine in 95-100% yield.
CATALYTIC REACTIONS
[0114] The instant application sets forth methods of catalyzing chemical reactions, wherein the methods include contacting a complex, set forth herein, with suitable reagents for the
chemical reaction to occur. In some embodiments, the chemical reaction catalyzed is olefin polymerization. In some other embodiments, the chemical reaction catalyzed is
hydroamination. In some other embodiments, the chemical reaction catalyzed is cross coupling. In some other embodiments, the chemical reaction catalyzed is hydrogenation.
[0115] The literature describing Au-based catalysts includes a) H. Schmidbaur, et al, B: J. Chem. Sci. 2011, 66, 329-350; Synthesis (Eds.: A.S.K. Hashmi, F. D. Toste), Wiley-VCH, Weinheim, 2012; A. Gomez-Suarez, et al, Angew. Chem. 2012, 124, 8278-8281; Angew. Chem. Int. Ed. 2012, 51, 8156-8159; C. C. J. Loh, et al, Chem. Eur. J. 2012, 18, 10212- 10225; D. Garayalde, et al, ACS Catal. 2012, 2, 1462-1479; D. Wang, et al, J. Am. Chem. Soc. 2012, 134, 9012-9019; f) B.-L. Lu, L. Dai, M. Shi, Chem. Soc. Rev. 2012, 41, 3318- 3339; L.-P. Liu, et al, Chem. Soc. Rev. 2012, 41, 3129-3139; M. Rudolph, et al, Chem. Soc. Rev. 2012, 41, 2448-2462; C. D. Pina et al, Chem. Soc. Rev. 2012, 41, 350-369; M.
Rudolph, et al, Chem. Commun. 201 1, 47, 6536-6544; M. Bandini, Chem. Soc. Rev. 2011, 40, 1358-1367; M. Malacria, , Top. Curr. Chem. 201 1, 302, 157-182; A. S. K. Hashmi, Angew. Chem. 2010, 122, 5360-5369; Angew. Chem. Int. Ed. 2010, 49, 5232-5241 ; D. J. Gorin, et al, Chem. Rev. 2008, 108, 3351-3378.
[0116] The literature describing hydroamination reactions includes J. L. Klinkenberg, et al, Angew. Chem. 2011, 123, 88-98; Angew. Chem. Int. Ed. 2011, 50, 86-95; I. Krossing, Angew. Chem. 201 1, 123, 1 1781-1 1783; Angew. Chem. Int. Ed. 2011, 50, 11576-11578; T. E. Muller, et al, Chem. Rev. 2008, 108, 3795-3892; R. A. Widenhoefer, et al, Eur. J. Org. Chem. 2006, 2006, 4555-4563.
[0117] The literature describing gold catalyzed hydroamination of alkynes includes S. Fleischer, et al, Chem. Eur. J. 2012, 18, 9005-9010; E. Alvarado, et al, Chem. Eur. J. 2012, 18, 121 12-12121; R. Kinjo, et al, Angew. Chem. 201 1, 123, 5674-5677; Angew. Chem. Int. Ed. 2011, 50, 5560-5563; K. L. Butler, et al, Angew. Chem. 2012, 124, 5265-5268; Angew. Chem. Int. Ed. 2012, 51, 5175-5178; K. D. Hesp, et al, J. Am. Chem. Soc. 2010, 132, 18026- 18029; A. Leyva-Perez, et al, J. Org. Chem. 2010, 75, 7769-7780; V. Lavallo, et al, Angew. Chem. 2008, 120, 5302-5306; Angew. Chem. Int. Ed. 2008, 47, 5224-5228; E. Mizushima, et al, Org. Lett. 2003, 5, 3349-3352)
[0118] In some embodiments, the instant application provides methods of catalyzing olefin polymerization reactions comprising contacting a complex described herein with suitable olefin polymerization reagents.
[0119] In some embodiments, the instant application provides methods of catalyzing hydroaddition reactions comprising contacting a complex described herein with suitable hydroaddition reagents.
[0120] In some embodiments, the instant application provides methods of catalyzing hydroamination reactions comprising contacting a complex described herein with suitable hydroamination reagents.
[0121] In some embodiments, the instant application provides methods of catalyzing cross coupling reactions contacting a complex described herein with suitable cross coupling reagents.
[0122] In some embodiments, the instant application provides methods of catalyzing olefin metathesis reactions comprising contacting a complex described herein with suitable olefin metathesis reagents.
[0123] In some embodiments, the instant application provides methods of catalyzing hydroformylation reactions comprising contacting a complex described herein with suitable hydroformylation reagents.
[0124] In some embodiments, the instant application provides methods of catalyzing hydrogenation reactions comprising contacting a complex described herein with suitable hydrogenation reagents.
[0125] In some embodiments, the instant application provides methods of catalyzing hydroaminomethylation reactions comprising contacting a complex described herein with suitable hydroaminomethylation reagents.
EXAMPLES
[0126] Example 1 - Synthesis of Ligands
[0127] A solution of the C-H carba-c/oso-dodecaborate anion in THF was treated with 1-3 equivalents of a base (most preferably w-BuLi) and stirred for 3 hours and subsequently concentrated under high vacuum. The residue was thoroughly washed with dry hexane and the solid was subsequently dissolved in THF or F-C6H5 and treated with 1.1 equivalents of the desired X-P(R2)(R3) reagent and the reaction was stirred until completion was determined by 31P NMR analysis. The mixture was subsequently concentrated to dryness, washed with hexane, and the solid residue containing the phosphine ligand extracted with a solvent ( e.g. CHC13, CH2C12, F-C6H5) where the salt byproducts do not dissolve. The
mixture was filtered and the solution was concentrated to dryness to afford the desired phosphine in 95-100% yield.
[0128] Ligands synthesized by this method include the following examples:
[0129] iPr2PCBnClif Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =77.3 ppm
[0130] iPr2PCBnH5Cl6 " Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =86.6 ppm
[0131] iPrzPCBnHn" Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ = 45.4 ppm
[0132] iPrzPCBnHn" N(Butyl4)+; 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =45.6 ppm
[0133] iPrzPCBnHn" N(Me4)+; 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =45.6 ppm
[0134] iPrzPCBnBrn" Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =100.2 ppm
[0135] iPr2PCBnH5Br6 " Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =95.0 ppm
[0136] PhzPCBnBrn" Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ = 106.6 ppm
[0137] Ph2PCBiiClu " Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ = 87.8 ppm
[0138] Et2PCBiiBrn" Li+ (x 4 THF); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C) δ =99.7 ppm
[0139] Example 2 - Synthesis of a Catalyst
[0141] A solution of the phosphine ligand iPr2PCBnCln" Li (x 4 THF) (1 mmol, 933.421 mg) was dissolved in 20 mL FC6H5 and reacted with a solution of (ClPdAllyl)2 (0.5 mmol 182.94 mg) that was dissolved in 10 mL of FC6H5. The resulting mixture was stirred and a precipitate of LiCl and the desired complex rapidly formed. After 15 minutes the precipitate was collected and washed with 10 mL of FC6H5. The desired complex was extracted from the LiCl precipitate with 100 mL of CH2CI2, filtered, and the remaining solid LiCl discarded. The CH2CI2 solution was concentrated under high vacuum to afford the desired complex in 95% yield (0.95 mmol, 746.3 mg).
[0142] ¾ NMR (300 MHz, CD2C12, 25 °C): 6=5.78 (m, 1H), 4.92 (s-br, 2H), 3.74 (s-br, 2H), 3.53 (m, 2H), 1.52 (m, 12H); ^P-^H-dec) NMR (121 MHz, CD2C12, 25 °C):
6=1 17.61 ; 13C MR (100 MHz, CD2C12, 25 °C): 6=119.41 , 29.85, 27.17, 22.58; "B-^H- dec) NMR (96 MHz, CD2C12, 25 °C): 6= 1.38, -7.48, -9.60 ppm.
[0143] Example 3 - Olefin Polymerization
[0144] The catalyst above (0.01 mmol) was dissolved in CH2CI2. Subsequent addition of norbornene (1 mmol) monomer and stirring the mixture for 1 hour, afforded polynorbomene in 82% yield. The polymer was isolated by the addition of methanol to the mixture, whereupon the polymer precipitated.
[0145] Example 4 - Synthesis of a Catalyst
COD
[0147] A solution of the phosphine ligand iPr2PCBnCln" Li (x 4 THF) (1 mmol, 933.421 mg) dissolved in 20 mL FC6¾ was reacted with a solution of (ClIr(COD))2 (0.5 mmol 335.85 mg) dissolved in 40 mL of FC6H5. The mixture was stirred for 24 hours and a precipitate of LiCl formed. The solution was filtered and concentrated under high vacuum to afford the desired complex in 100% yield (1.0 mmol, 938.5 mg). Structure was confirmed by single crystal diffraction study and NMR 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C): 6=100.54 ppm
[0148] Example 5 - Olefin Hydrogenation
[0149] Procedure: The catalyst above (0.1 mmol) was dissolved in a solution of cyclooctene (2 mmol)/5 mL THF. The mixture was exposed to 1 atmosphere of hydrogen gas and heated to 25°C for 30 minutes. XH NMR analysis of the mixture revealed complete hydrogenation of cyclooctene to afford cyclooctane in quantitative yield (2 mmol, 100%).
[0150] Example 6 - Synthesis of a Catalyst
COD = 1 ,4-cyclooctadiene
[0152] Synthesis of PdCH3(COD)iPr2PCB11H5Br6 A solution of iP^PCBnHsBre" Li+ (x 4 THF) (774.78 mg, 1.0 mmol) in THF, was combined with a solution of PdCH3Cl(COD) (265.1 mg, 1 mmol) in THF and the reaction mixture was allowed to stir for 1 hour. Lithium Chloride was precipitated out by the addition of CHCI3 and the solution filtered. Volatiles were removed under reduced pressure and washed with hexanes (2 x 2mL). The zwitterionic complex 2 was obtained as a light yellow colored powder (694.82 mg, 98 % yield). XH NMR (300 MHz, CD2C12, 25 °C): 6=5.89 (m, 2H), 5.39 (m, 2H), 2.68 (m, 4H) 2.54 (m, 4H), 2.38 (m, 2H), 1.48 (m, 12H), 1.31 (s, 3H); 31P-(1H-dec) NMR (121 MHz, CD2C12, 25 °C):
6 = 68.32
[0153] Example 7 - Olefin Polymerization
spersity
[0154] The catalyst above (0.1 mmol) was dissolved in CH2C12. Subsequent addition of monomer (1 mmol) and stirring the mixture for 1 hour, afforded polynorbornene (98% yield)
and Polycyclooctene (93% yield), respectively. The polymer was isolated by the addition of methanol to the mixture, whereupon the polymer precipitated. Analysis of the material by Gel permeation chromatography reveals a very low polydispersity of 1.048 (polynorbomene) and 1.056 (polycyclooctene) and an average molecular weight of approximately 12,000. These data indicate that the catalyst is quite active.
[0155] Example 8 - Synthesis of a Catalyst
[0156] This catalyst is suitable for use in, for example, olefin polymerization
[0158] A solution of iPr2PCBnH5Br6 " Li+ (x 4 THF) ( 1 (774.78 mg, 1.0 mmol) in THF, was combined with a solution of PdCH3Cl(COD) (265.1 mg, 1 mmol) in THF and the reaction mixture was allowed to stir for 1 hour. Volatiles were removed under reduced pressure and washed with hexanes (2 x 2mL) to afford the complex in quantitative yield (1 mmol, 1.039 g). 31P-(1H-dec) NMR (121 MHz, THF, 25 °C): δ = 71.30 ppm.
[0159] Example 9 - Olefin Polymerization
[0160] The catalyst above (0.1 mmol) was dissolved in THF. Subsequent addition of norbomene (1 mmol) monomer and stirring the mixture for 4 hours, afforded polynorbomene in 95% yield. The polymer was isolated by the addition of methanol to the mixture, whereupon the polymer precipitated.
[0161] Example 10 - Synthesis of a Catalyst
[0162] This catalyst is suitable for use in, for example, Pd-catalyzed cross-coupling.
[0163] Synthesis of Pd(iPr2PCBnH5Br6)2" 2Li+(x 4 THF). A solution of iPr2PCBuH5Br6 Li+ (x 4 THF) (774.78 mg, 1.0 mmol) in THF, was combined with a solution of (CH3)2Pd (COD) (123.0 mg, 0.5 mmol) in THF and the reaction mixture was allowed to stir for 1 hour. Volatiles were removed under reduced pressure to afford the desired dianionic Pd(0) complex a dark colored (828.0 mg, 100 % yield). The structure was confirmed by a preliminary X-ray diffraction study and NMR. ^P-^H-dec) NMR (121 MHz, THF, 25 °C): δ = 53.41 ppm.
[0164] Example 11 - Pd Cross-coupling (alpha arylation of ketones)
[0165] The catalyst above (0.1 mmol) was dissolved in THF. Subsequent addition of the ketone (1 mmol), chlorobenzene (1 mmol) and NaOtBu (1.05 mmol) followed by heating at 80°C for 6 hours, afforded the desired alpha-arylated ketone in 89% yield as indicated by 1H NMR spectroscopy.
[0166] Example 12 - Synthesis of a Catalyst
[0167] This catalyst is suitable for use in, for example, olefin hydrogenation
COD = 1 ,4-cyclooctadiene
[0168] Synthesis of anionic ClIr(COD)[P(C3H7)2CB11H11]: P(C3H7)2(CB11H11)" N(Butyl)4 +
(501.6 mg, 1 mmol) in benzene (5 mL) was added to a benzene (5 mL) solution of
(Ir(COD)Cl)2 (335.8 mg, 0.5 mmol) and allowed to stir overnight. The mixture was concentrated under vacuum and washed with hexanes (2 x 5mL), to afford the desired anionic complex as a yellow-orange solid in 100% yield (837.4 mg, lmmol mmol). 31P NMR (242 MHz, C6D6, 25 °C): 6=37.46 ppm.
[0169] Example 13 - Olefin Hydrogenation
[0170] Procedure: The catalyst above (0.1 mmol) was dissolved in a solution of cyclooctene (1 mmol)/5 mL THF. The mixture was exposed to 1 atmosphere of hydrogen gas and heated to 50°C for 2 hours. XH NMR analysis of the mixture revealed complete hydrogenation of cyclooctene to afford cyclooctane in quantitative yield (1 mmol, 100%).
[0171] Example 14 - Hydrogenation
[0172] Procedure: The catalyst above (0.1 mmol) was dissolved in a solution of cyclooctene (2 mmol)/5 mL THF. The mixture was exposed to 1 atmosphere of hydrogen gas and heated to 40°C for 1 hour. XH NMR analysis of the mixture revealed complete hydrogenation of cyclooctene to afford cyclooctane in quantitative yield (2 mmol, 100%).
[0173] Example 15 - Synthetic Procedure
[0174] This Example shows a synthesis of a phosphine bearing the CBnClif moiety, (iPr)2P(CBiiClii)"Li+. This group is advantageous because it is very large and the intermediate steric bulk of the isopropyl groups allow the phosphorus lone pair to be accessible for coordination. The trimethyl ammonium salt of anion 1 with 2 (in Figure 1) was treated with equivalents of w-BuLi and subsequent quenched with the dianionic
intermediate with ClP(iPr)2 afforded 2 in 98% yield (Figure 1). Anionic phosphine 2 is very soluble in common polar solvents (CH2CI2, CHCI3, THF), and is not sensitive to oxygen in solution or the solid state. The XH NMR of 2 displays two distinct doublets of doublets for the CH3 isopropyl groups, indicating hindered rotation about the P-iPr bonds. A single crystal X- ray diffraction study shows a sterically congested environment around the pyramidalized (sum of CPC angles = 325.1°) phosphorus center (Figure 2). The phosphorus bond to the carborane hypercarbon (P-Cl = 1.9376(16)A) is significantly longer than the P-iPr bonds (P- C2 = 1.8679(19), P-C3 = 1.8636(18)A). The lithium countercation of 2 is coordinated by four THF molecules and does not associate with the phosphorus lone pair or pendant charged carborane R-group (closest CI distance to Li = 4.283 A). This observation suggests that the phosphorus lone pair is available for binding other metals and that the weakly coordinating nature of the CBnCn R-group remains intact.
[0175] Anionic phosphine 2 (in Figure 1) was reacted with ClAu(THT) in fluorobenzene at RT, and within 5 minutes a large amount of white precipitate formed . Analysis of the precipitate by 31P NMR in CD2CI2 shows a phosphorus resonance at +90 ppm, which is significantly shifted down field from the starting material 2 (+77 ppm), and in line with the formation of a Au-phosphine complex. The XH-NMR spectra clearly shows resonances corresponding to the phosphine ligand as well as coordinated THT, which suggests the formation of the zwitterionic Au complex 3(THT) (Figure 3) formed via ligand coordination and anion metathesis . The driving force for the anion metathesis is the insolubility of LiCl in F-benzene. A single crystal X-ray diffraction study confirms the structure of 3(THT If the reaction is performed in THF, a solvent where LiCl is soluble, THT is liberated and an unusual anionic ClAu-Li+ complex 3 (LiCl) is isolated. Complex 3 (LiCl) can also be prepared by the treatment of isolated 3(THT) with LiCl in THF. In contrast to 3(THT) it was possible to grow single crystals of 3 (LiCl) without significant disorder and thus examined the solid state structural aspects of this molecule. The Tolman cone angle for the AP -phosphine ligand is 204°, which indicates it is much more bulky than a standard sterically demanding phosphine ligand, such as P(t-Bu)3 (cone angle = 182°). The P-Au bond length is 2.2477(12) A, which is close to a neutral ortho-dicarbaclosodecaborane substituted phosphine AuCl complex (2.232(3) A). The anionic CBnCln R-group displays one chloride interaction with the Au ion (closest Au....Cl-B distance = 3.118 A), which is outside the sum of the covalent Au/Cl radii but in range of a van der Waals contact (sum of Au/Cl vdW radii = 3.41 A). For comparison, the chloride ligand (trans from the phosphine) is at a distance of 2.2883(12) A from the metal center. Hence, the carborane substituent retains a significant amount of
weakly coordinating character, even though it is forced into a position close to the metal center.
[0176] Example 16 - Hydroamination
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
[0178] Yields not in brackets, were measured by NMR via direct integration of the alkyne consumed versus the imine product formed, and reflect the average of two catalytic runs. No side reactions were observed. Number in brackets after the NMR yield indicate isolated yield.
[0179] This Example demonstrates the catalytic properties of complexes 3 in the hydroamination of primary amines with alkynes. This example observed the addition of aniline to phenyl acetylene. A 1 : 1 neat mixture of amine and alkyne was added to 0.1 mol% of complex 3(ΤΗΤ>, where upon an exothermic reaction occurred. Monitoring the reaction by lH NMR revealed the hydroamination was >95% complete in 1 hour (entry 1, Table 1). Identical results were obtained with 3(LiCl), (entry 2, Table 1), hence further catalytic tests were carried out using exclusively 3(THT). Reducing the catalyst loading to 0.01% and heating the mixture at 50°C for 16 hour does not reduce the yield of the imine (entry 3, table 1). Even at a catalyst loading of 0.004%, the imine is formed in excellent yield (88%), which corresponds to a catalyst turn over number (T.O.N.) of 22,000 (entry 4, table 1). The highest reported T.O.N, for the Au-catalyzed hydroamination of an alkyne with a primary amine is around 9000, using a multicomponent acid activated Au system. Control experiments with ClAu(THT), or HCBnCln-Cs+/ClAuTHT at low catalyst loading (0.1mol%) afforded the
imine in only trace amounts (<5%). A metal free Bronsted acid catalyzed pathway can also be ruled out since (iPr)2P(CBnCln)- I¾NPh+ does not catalyse the reaction. Since such high catalytic activity is extremely unusual for Au catalyzed reactions, this Example observed the hydroamination of phenyl acetylene with several different aryl amines at ultra-low loading (0.001%, 10 ppm). After 24 hours mesityl amine effectively reacts to afford the
corresponding imine in 67% yield (T.O.N. = 67,000) (entry 5, table 1). Bulkier 2,6- diisopropylphenylamine (Dipp-amine) is even more efficient in the reaction, affording the analogous imine in 85% yield (T.O.N. = 85,000) (entry 6, table 1). For the latter reaction, the catalyst is also fast, displaying an initial Turn Over frequency of 29,000 in the first hour. Even higher T.O.N.s are obtained for the analogous reactions with 4-fluorophenylacetylene, reaching a maximum of 92,000 with Dipp-amine (entries 7-9, table 1). Results with 4- methoxyphenylacetylene were better than most, where the catalyst converted all three amines to the corresponding imines with T.O.N.s of 90,000 or greater (entries 10-12). The trend in increased reactivity with amine steric bulk is likely related to the decreased binding ability of bulkier amines, and the ensuing imines, which allows for more facile ligand exchange at the Au center. Catalyst 3(THT) is also effective for the hydroamination of aryl amines with diaryl substituted (entries 13-15, table 1), and terminal alkyl alkynes (entries 15-18, table 1). Although the activity is lower in these cases the performance of 3(THT) compares favorably with typical Au catalysts, which often require catalyst loadings of l-10mol%. At low catalyst loading (0.2 mol%), and using internal dialkylalkynes (3-hexyne) or an alkyl amine (t- BuNH2) as substrates produced the expected imines only in trace amounts (<5%).
[0180] The two mechanisms generally proposed for Au catalyzed hydroamination either involve a direct addition of the amine to a coordinated alkyne or a coordination insertion mechanism. In either pathway, charged intermediates exist that undergo proton transfer steps that lead to the formation of the functionalized amine. It is clear that the pendant anionic CBnClii group of AP-phosphine 2 is beneficial for the reaction sequence. If industrial scale applications are to be realized for homogenous Au catalysis, as well as systems utilizing other precious metals, it is necessary to have catalysts, such as complexes 3, available that are highly active and efficient. Many transition metal catalyzed processes involve cationic intermediates that might benefit from the use of an AP-ligand.
[0181] Although the foregoing invention has been described in some detail by way of illustration and example for purposes of clarity of understanding, one of skill in the art will appreciate that certain changes and modifications may be practiced within the scope of the appended claims. In addition, each reference provided herein is incorporated by reference in
its entirety to the same extent as if each reference was individually incorporated by reference. Where a conflict exists between the instant application and a reference provided herein, the instant application shall dominate.
Claims
WHAT IS CLAIMED IS:
1. A composition comprising a transition metal and a phosphine lig comprising at least one carba-closo-dodecaborate substituent.
2. A ligand having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy; and
A is a cation.
3. A composition comprising:
a solvent selected from the group consisting of dimethoxy ethane, dioxane, pyridine, tetrahydrofuran, diethyl ether, benzene, toluene, acetonitrile, methylene chloride, chloroform, dimethyl formamide, and acetone;
a ligand of claim 2; and
a transition metal selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
4. The composition of claim 3, wherein the transition metal is selected from the group consisting of Fe, Ru, Co, Ni, and Pd.
5. The ligand of claim 2, wherein R1 is a halogen selected from the group consisting of F, CI, Br, and I.
6. The ligand of claim 2, wherein A is selected from the group consisting of Li, Na, K, Cs, HN(alkyl)3, N(alkyl)4, Mg, Ca, and Zn.
7. The ligand of claim 2, wherein R1 is H.
8. The ligand of claim 2, wherein R is CI.
9. The ligand of claim 2, wherein R is Br.
The ligand of claim 2, wherein R is I.
1 1. The ligand of claim 2, wherein R is alkyl.
The ligand of claim 2, wherein R is alkoxy.
The ligand of claim 2, wherein R is siloxy.
14. The ligand of claim 2, wherein R1 comprises two or more different types of substituents selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy.
The ligand of claim 2, wherein R1 comprises combinations of H and halogen.
The ligand of claim 2, wherein the ligand has a structure selected from the group consisting
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
X1 is selected from the group consisting of H, alkyl, aryl, halide, alkoxy, and
NR4R5;
L is neutral ligand;
subscript n is an integer selected from the group consisting of 1, 2, 3, 4, 5, and
6; and
M is a transition metal.
18. The complex of 17, wherein R2 and R3 are isopropyl.
19. The complex of 17, wherein n is 1.
20. The complex of 17, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
21. The complex of claim 20, wherein M is selected from the group consisting of Fe, Ru, Co, Ni, and Pd.
A zwitterionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
X1 is selected from the group consisting of H, alkyl, aryl, halide, alkoxy, and
NR4R5;
Q is a chelating ligand; and
M is a transition metal.
23. The complex of claim 22, further comprising 1 to 2 additional Q chelating ligands bonded to M.
24. The complex of claim 22, wherein R2 and R3 are isopropyl.
25. The complex of 22, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
26. The complex of claim 22, wherein M is selected from the group consisting of Fe, Ru, Co, Ni, and Pd.
An anionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
X1 is selected from the group consisting of H, alkyl, and aryl;
X2 is an anion selected from the group consisting of H, halide, alkyl, aryl, halide, alkoxy, and R4R5;
A is a cation;
L is neutral ligand;
subscript n is an integer selected from the group consisting of 1, 2, 3, 4, 5, and
6; and
M is a transition metal.
28. The complex of claim 27, wherein n is 1.
29. The complex of 27, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
30. The complex of claim 27, wherein M is selected from the group consisting of Fe, Ru, Co, Ni, and Pd.
31. An anionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
X1 is selected from the group consisting of H, alkyl, and aryl;
X2 is an anion selected from the group consisting of H, halide, alkyl, aryl, halide, alkoxy, and R4R5;
Q is a chelating ligand; and
A is a cation; and
M is a transition metal.
32. The complex of claim 31, further comprising 1 to 2 additional Q ligands bonded to M.
33. The complex of claim 31, wherein A is selected from the group consisting of Li, Na, K, Cs, HN(alkyl)3, and N(alkyl)4.
34. The complex of 31, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
35. The complex of claim 31, wherein M is selected from the group consisting of Fe, Ru, Co, Ni, and Pd.
A zwitterionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
L is neutral ligand;
subscript n is an integer selected from the group consisting of 1, 2, 3, 4, 5, and
6; and
M is a transition metal.
37. The complex of 36, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
38. The complex of claim 36, wherein M is selected from the group consisting of Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
39. The complex of 36, wherein n is 1.
A zwitterionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
M is a transition metal.
41. The complex of 40, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
42. The complex of claim 40, wherein M is selected from the group consisting of Ni, Pd, and Cu.
43. The complex of claim 40, wherein M is in either a +2 or +4 oxidation state.
An anionic complex having the following structure:
wherein R1 is selected from the group consisting of H, halogen, alkyl, aryl, silyl, and alkoxy;
R2 and R3 are each independently selected from the group consisting of alkyl, aryl, alkoxy, and NR4R5; and
R4 and R5 are each independently selected from the group consisting of alkyl, aryl, and alkoxy;
A is a cation;
subscript y is an integer selected from the group consisting of 1 and 2; and M is a transition metal.
45. The complex of 44, wherein A is a monopositively charged cation or a dipositively charged cation.
46. The complex of 44, wherein A is a dipositively charged cation and subscript y is 1.
47. The complex of 44, wherein A is a monopositively charged cation and subscript y is 2.
48. The complex of 44, wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au.
49. The complex of claim 44, wherein M is selected from the group consisting of Ni, Pd, and Cu.
The complex of claim 44, wherein M is in either a +2 or +4 oxidation state.
51. A complex comprising the ligand of claim 2 and a transition metal.
The complex of claim 51 , wherein the transition metal
53. A complex having the structure selected from the group consisting of :
54. A method of polymerizing olefins, comprising contacting a complex of claim 17, 22, 27, or 31, with reagents suitable for olefin polymerization
55. A method of hydroaddition, comprising contacting a complex of claim
36
A method of cross coupling, comprising contacting a complex of claim
40 or 44.
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EP13850907.0A EP2914606B1 (en) | 2012-11-05 | 2013-11-05 | Complexes of phosphine ligands comprising a carba-closo-dodecaborate substituent |
US14/440,566 US20150299234A1 (en) | 2012-11-05 | 2013-11-05 | Complexes of phosphine ligands comprising a carba-closo-dodecaborate substituent |
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US201261722740P | 2012-11-05 | 2012-11-05 | |
US61/722,740 | 2012-11-05 |
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CN111868064A (en) * | 2017-10-31 | 2020-10-30 | 陶氏环球技术有限责任公司 | Catalyst system comprising carborane co-catalyst |
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CN111450886A (en) * | 2019-01-22 | 2020-07-28 | 中国科学院上海高等研究院 | Catalyst for catalyzing alkyne to generate trans-olefin and preparation method and application thereof |
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- 2013-11-05 EP EP13850907.0A patent/EP2914606B1/en active Active
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Non-Patent Citations (46)
Title |
---|
"Synthesis", 2012, WILEY-VCH |
A. A. TYUTYUNOV ET AL., RUSSIAN CHEMICAL BULLETIN INTERNATIONAL EDITION, 1 November 2008 (2008-11-01), pages 2307 - 2310 |
A. GOMEZ-SUAREZ ET AL., ANGEW. CHEM., vol. 124, 2012, pages 8278 - 8281 |
A. LEYVA-PEREZ ET AL., J. ORG. CHEM., vol. 75, 2010, pages 7769 - 7780 |
A. M. SPOKOYNY ET AL., NATURE CHEM., vol. 3, 2011, pages 590 - 596 |
A. S. K. HASHMI, ANGEW. CHEM., vol. 122, 2010, pages 5360 - 5369 |
ALEXANDER HIMMELSPACH ET AL.: "Microwave-Assisted Kumada-Type Cross-Couplin g Reactions of Iodinated Carba-closo-dodecaborate Anions", INORG. CHEM., vol. 51, no. 4, 26 January 2012 (2012-01-26), pages 2679 - 2688, XP055254476 * |
ANGEW. CHEM. INT. ED., vol. 47, 2008, pages 5224 - 5228 |
ANGEW. CHEM. INT. ED., vol. 49, 2010, pages 252 - 255 |
ANGEW. CHEM. INT. ED., vol. 49, 2010, pages 5232 - 5241 |
ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 11576 - 11578 |
ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 5560 - 5563 |
ANGEW. CHEM. INT. ED., vol. 50, 2011, pages 86 - 95 |
ANGEW. CHEM. INT. ED., vol. 51, 2012, pages 5175 - 5178 |
ANGEW. CHEM. INT. ED., vol. 51, 2012, pages 8156 - 8159 |
B.-L. LU; L. DAI; M. SHI, CHEM. SOC. REV., vol. 41, 2012, pages 3318 - 3339 |
C. C. J. LOH ET AL., CHEM. EUR. J., vol. 18, 2012, pages 10212 - 10225 |
C. D. PINA ET AL., CHEM. SOC. REV., vol. 41, 2012, pages 350 - 369 |
D. GARAYALDE ET AL., ACS CATAL., vol. 2, 2012, pages 1462 - 1479 |
D. J. GORIN ET AL., CHEM. REV., vol. 108, 2008, pages 3351 - 3378 |
D. WANG ET AL., J. AM. CHEM. SOC., vol. 134, 2012, pages 9012 - 9019 |
E. ALVARADO ET AL., CHEM. EUR. J., vol. 18, 2012, pages 12112 - 12121 |
E. MIZUSHIMA ET AL., ORG. LETT., vol. 5, 2003, pages 3349 - 3352 |
H. SCHMIDBAUR ET AL.: "B: J. Chem. Sci.", vol. 66, 2011, pages: 329 - 350 |
I. KROSSING, ANGEW. CHEM., vol. 123, 2011, pages 11781 - 11783 |
J. I. VAN DER VLUGT, ANGEW. CHEM., vol. 122, 2010, pages 260 - 263 |
J. L. KLINKENBERG ET AL., ANGEW. CHEM., vol. 123, 2011, pages 88 - 98 |
K. D. HESP ET AL., J. AM. CHEM. SOC., vol. 132, 2010, pages 18026 - 18029 |
K. L. BUTLER ET AL., ANGEW. CHEM., vol. 124, 2012, pages 5265 - 5268 |
L.-P. LIU ET AL., CHEM. SOC. REV., vol. 41, 2012, pages 3129 - 3139 |
M. BANDINI, CHEM. SOC. REV., vol. 40, 2011, pages 1358 - 1367 |
M. MALACRIA, TOP. CURR. CHEM., vol. 302, 2011, pages 157 - 182 |
M. RUDOLPH ET AL., CHEM. COMMUN., vol. 47, 2011, pages 6536 - 6544 |
M. RUDOLPH ET AL., CHEM. SOC. REV., vol. 41, 2012, pages 2448 - 2462 |
M. SCHOLZ ET AL., CHEM. REV., vol. 111, 2011, pages 7035 - 7062 |
MATTHEW J. NAVA ET AL.: "High Yield C-Derivatization of Weakly Coordinating Carborane Anions", INORG CHEM., vol. 49, no. 11, 7 June 2010 (2010-06-07), pages 4726 - 4728, XP055251777 * |
N. FEY ET AL., ORGANOMETALLICS, vol. 31, 2012, pages 2907 - 2913 |
R. A. WIDENHOEFER ET AL., EUR. J. ORG. CHEM., vol. 2006, 2006, pages 4555 - 4563 |
R. KINJO ET AL., ANGEW. CHEM., vol. 123, 2011, pages 5674 - 5677 |
ROSARIO NUUEZ ET AL.: "Coordination of the nido-carboranyldiphosphine liga nd to ruthenium(II): the first example of the tricoordinating capacity of th e 7,8-(PPh2)2-7,8-C2B9H10 moiety", APPL. ORGANOMETAL. CHEM., vol. 17, 2003, pages 509 - 717, XP055254128 * |
S. FLEISCHER ET AL., CHEM. EUR. J., vol. 18, 2012, pages 9005 - 9010 |
S. KORBE ET AL., CHEM. REV., vol. 106, 2006, pages 5208 - 5249 |
See also references of EP2914606A4 |
T. E. MULLER ET AL., CHEM. REV., vol. 108, 2008, pages 3795 - 3892 |
V. LAVALLO ET AL., ANGEW. CHEM., vol. 120, 2008, pages 5302 - 5306 |
WEIXING GU ET AL.: "Improved methods for the halogenation of the [HCB11H11] - anion", CHEM. COMMUN., vol. 46, 2010, pages 2820 - 2822, XP055254489 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111868064A (en) * | 2017-10-31 | 2020-10-30 | 陶氏环球技术有限责任公司 | Catalyst system comprising carborane co-catalyst |
JP2021505696A (en) * | 2017-10-31 | 2021-02-18 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst system containing carborane cocatalyst |
US11572375B2 (en) | 2017-10-31 | 2023-02-07 | Dow Global Technologies, Llc | Catalyst systems comprising carborane cocatalysts |
JP7377796B2 (en) | 2017-10-31 | 2023-11-10 | ダウ グローバル テクノロジーズ エルエルシー | Catalyst systems containing carborane cocatalysts |
Also Published As
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EP2914606B1 (en) | 2019-07-03 |
EP2914606A4 (en) | 2016-05-25 |
EP2914606A1 (en) | 2015-09-09 |
US20150299234A1 (en) | 2015-10-22 |
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