WO2015077306A1 - Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation - Google Patents
Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation Download PDFInfo
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- WO2015077306A1 WO2015077306A1 PCT/US2014/066356 US2014066356W WO2015077306A1 WO 2015077306 A1 WO2015077306 A1 WO 2015077306A1 US 2014066356 W US2014066356 W US 2014066356W WO 2015077306 A1 WO2015077306 A1 WO 2015077306A1
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- Prior art keywords
- substituted
- aryl
- group
- alkyl
- complex
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000006459 hydrosilylation reaction Methods 0.000 title claims abstract description 59
- 238000010542 dehydrogenative silylation reaction Methods 0.000 title abstract description 39
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 19
- 239000010941 cobalt Substances 0.000 title abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 18
- -1 cobalt terpyridine complexes Chemical class 0.000 claims abstract description 36
- 125000003118 aryl group Chemical group 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 230000008569 process Effects 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 41
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 34
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 32
- 150000002431 hydrogen Chemical group 0.000 claims description 30
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 29
- 125000005842 heteroatom Chemical group 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 125000003107 substituted aryl group Chemical group 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000004122 cyclic group Chemical group 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 125000005915 C6-C14 aryl group Chemical group 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 229910007161 Si(CH3)3 Inorganic materials 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 5
- 125000005346 substituted cycloalkyl group Chemical group 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000005394 methallyl group Chemical group 0.000 claims description 4
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 125000005023 xylyl group Chemical group 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000003446 ligand Substances 0.000 abstract description 21
- 150000001868 cobalt Chemical class 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 83
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 40
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical compound N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000006884 silylation reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 150000004696 coordination complex Chemical class 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 8
- XAYDWGMOPRHLEP-UHFFFAOYSA-N 6-ethenyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCCC2OC21C=C XAYDWGMOPRHLEP-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 150000004700 cobalt complex Chemical class 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 125000000746 allylic group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 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 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000001181 organosilyl group Chemical class [SiH3]* 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 2
- IVHZIUZQMOBVHT-UHFFFAOYSA-N 2-dimethylsilylethyl(trimethyl)silane Chemical compound C[SiH](C)CC[Si](C)(C)C IVHZIUZQMOBVHT-UHFFFAOYSA-N 0.000 description 2
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 125000000743 hydrocarbylene group Chemical group 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- NWRZGFYWENINNX-UHFFFAOYSA-N 1,1,2-tris(ethenyl)cyclohexane Chemical compound C=CC1CCCCC1(C=C)C=C NWRZGFYWENINNX-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- VXDHQYLFEYUMFY-UHFFFAOYSA-N 2-methylprop-2-en-1-amine Chemical compound CC(=C)CN VXDHQYLFEYUMFY-UHFFFAOYSA-N 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910010084 LiAlH4 Inorganic materials 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 description 1
- UOPTZAYKABCBRQ-UHFFFAOYSA-N cobalt pyridine Chemical compound [Co].c1ccncc1.c1ccncc1 UOPTZAYKABCBRQ-UHFFFAOYSA-N 0.000 description 1
- PLTOVEJYEUZSKT-UHFFFAOYSA-N cobalt;pyridine Chemical class [Co].C1=CC=NC=C1 PLTOVEJYEUZSKT-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 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 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 150000002194 fatty esters Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- WHJXGGISJBFSJJ-UHFFFAOYSA-N iron;pyridine Chemical compound [Fe].C1=CC=NC=C1 WHJXGGISJBFSJJ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- KVWLUDFGXDFFON-UHFFFAOYSA-N lithium;methanidyl(trimethyl)silane Chemical compound [Li+].C[Si](C)(C)[CH2-] KVWLUDFGXDFFON-UHFFFAOYSA-N 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- KEFOZNJTQPJEOB-UHFFFAOYSA-N pyridine-2,3-diimine Chemical compound N=C1C=CC=NC1=N KEFOZNJTQPJEOB-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229940024463 silicone emollient and protective product Drugs 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 125000004079 stearyl 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])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])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DAVGYCGZLQMNSH-UHFFFAOYSA-N triethoxy(octan-2-yl)silane Chemical compound CCCCCCC(C)[Si](OCC)(OCC)OCC DAVGYCGZLQMNSH-UHFFFAOYSA-N 0.000 description 1
- XVKXMTGNOIVVLP-UHFFFAOYSA-N triethyl(octyl)silane Chemical compound CCCCCCCC[Si](CC)(CC)CC XVKXMTGNOIVVLP-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- 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
- C07F15/06—Cobalt compounds
-
- 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
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
- C07F7/0878—Si-C bond
- C07F7/0879—Hydrosilylation reactions
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/14—Other (co) polymerisation, e.g. of lactides or epoxides
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- This invention relates generally to transition metal-containing compounds, more specifically to cobalt complexes containing terpyridine ligands and their use as catalysts for hydrosilylation and dehydrogenative silylation reactions.
- Hydrosilylation chemistry typically involving a reaction between a silyl hydride and an unsaturated organic group, is the basis for synthetic routes to produce commercial silicone -based products like silicone surfactants, silicone fluids and silanes as well as many addition cured products like sealants, adhesives, and coatings.
- Typical hydrosilylation reactions use precious metal catalysts to catalyze the addition of a silyl-hydride (Si-H) to an unsaturated group, such as an olefin.
- Si-H silyl-hydride
- an unsaturated group such as an olefin
- the resulting product is a silyl-substituted, saturated compound.
- the addition of the silyl group proceeds in an anti-Markovnikov manner, i.e., to the less substituted carbon atom of the unsaturated group.
- hydrosilylations only work well with terminally unsaturated olefins, as internal unsaturations are generally non-reactive or only poorly reactive.
- This reaction termed a dehydrogenative silylation, has potential uses in the synthesis of new silicone materials, such as silanes, silicone fluids, crosslinked silicone elastomers, and silylated or silicone-crosslinked organic polymers such as polyolefms, unsaturated polyesters, and the like.
- Various precious metal complex catalysts are known in the art including a platinum complex containing unsaturated siloxanes as ligands, which is known in the art as Karstedt's catalyst.
- Other platinum-based hydrosilylation catalysts include Ashby's catalyst, Lamoreaux's catalyst, and Speier's catalyst.
- U.S. Patent No. 5,955,555 discloses the synthesis of certain iron or cobalt pyridine di-imine (PDI) complexes bearing two anionic ligands. The preferred anions are chloride, bromide, and tetrafluoroborate.
- U.S. Patent No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic ligands containing a "pyridine" ring substituted with two imino groups.
- U.S. Patent Nos. 6,461,994, 6,657,026 and 7,148,304 disclose several catalyst systems containing certain transitional metal-PDI complexes.
- 7,053,020 discloses a catalyst system containing, inter alia, one or more bisarylimino pyridine iron or cobalt catalyst. Chirik et al describe bisarylimino pyridine cobalt complexes with anionic ligands (Inorg. Chem. 2010, 49, 6110 and JACS. 2010, 132, 1676.) However, the catalysts and catalyst systems disclosed in these references are described for use in the context of olefin hydrogenation, polymerizations and/or oligomerisations, not in the context of dehydrogenative silylation reactions.
- U.S. Patent No. 8,236,915 discloses hydrosilylation using Mn, Fe, Co, and Ni catalysts containing pyridinediimine ligands. However, these catalysts are sensitive to air and must be handled in a glove box.
- homogeneous metal catalysts suffer from the drawback that following consumption of the first charge of substrates, the catalytically active metal is lost to aggregation and agglomeration and its beneficial catalytic properties are substantially diminished via colloid formation or precipitation. This is a costly loss, especially for noble metals such as Pt.
- Heterogeneous catalysts are used to alleviate this problem but have limited use for polymers and also have lower activity than homogeneous counterparts.
- the two primary homogeneous catalysts for hydrosilylation, Speier's and Karstedt's often lose activity after catalyzing a charge of olefin and silyl- or siloxyhydride reaction. If a single charge of the homogeneous catalyst could be re -used for multiple charges of substrates, then catalyst and process cost advantages would be significant.
- the present invention provides a complex of the Formula:
- each occurrence of R 1 - R 11 is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R ⁇ R 11 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R !
- R 4 - R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, or an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
- R ! -R n are hydrogen.
- L is -C(R 22 ) 2 -Si(R 23 ) 3 where R 22 and R 23 are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
- the catal st is of the formula:
- R -R is chosen from an aryl group or a substituted aryl group.
- the substituted aryl group is chosen from tolyl, xylyl, naphthyl, mesityl, aniline, fluorophenyl, or a combination of two or more thereof.
- R ! -R 5 and R 7 -R n are hydrogen, and R 6 is chosen from pyrrolidino, flourophenyl, aniline, or mesityl.
- the complex is of the formula:
- the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof:
- each occurrence of R - R is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R ⁇ -R 11 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R !
- R 4 - R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, or an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
- R ! -R n are hydrogen.
- L is -C(R 22 ) 2 -Si(R 23 ) 3 where R 22 and R 23 are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
- R ! -R n are hydrogen.
- the catal st is of the formula:
- At least one of R ! -R n is chosen from an aryl group or a substituted aryl group.
- the substituted aryl group is aniline.
- the complex is of the formula:
- the process comprises removing the complex and/or derivatives thereof from the silylated product.
- the silylated product comprises a hydrosilylation product.
- the silylated product comprises a dehydrogenatively silylated product.
- the silylated product comprises a mixture of (i) a hydrosilylation product, and (ii) a dehydrogenative silylated product.
- the unsaturated compound (a) is chosen from a linear or branched olefin; a cycloalkene; an alkyl-capped allyl polyether; a vinyl-functional alkyl-capped allyl or methallyl polyether; an alkyl-capped terminally unsaturated amine; an alkyne; a terminally unsaturated acrylate or methacrylate; an unsaturated aryl ether; a vinyl-functionalized polymer or oligomer; a vinyl-functionalized and/or terminally-unsaturated alkenyl-functional silane; and/or silicone; an unsaturated fatty acid; an unsaturated ester; or combinations of two or more thereof.
- the reaction is conducted under an inert atmosphere.
- the reaction is carried out at a temperature of -10°C to 300°C.
- the silyl hydride comprises a hydride fluid chosen from one or a combination of compounds of the formulas:
- each R is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group;
- X is halogen, alkoxy, acyloxy, or silazane;
- m is 0-3;
- p is 1-3, with the proviso that the
- M represents a monofunctional group of formula R 3 SiOi /2 ;
- each occurrence of R is independently a Ci-Cig alkyl, a Ci-Cig substituted alkyl, a C6-C14 aryl or substituted aryl, wherein
- R optionally contains at least one heteroatom; subscripts a, b, c, d, e, f, and g are such that the
- the complex is immobilized on a support.
- the support is chosen from carbon, silica, alumina, MgCl 2 , zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.
- the present invention provides a composition produced by the process of claim 10, wherein the composition contains the catalyst or derivatives thereof.
- the composition comprises at least one component selected from the group of silanes, silicone fluids, and crosslinked silicones, or a combination of two or more thereof.
- the invention provides a complex of Formula (IV)
- each occurrence of R 1 - R 11 is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R ⁇ R 11 , other than hydrogen, optionally contain at least one heteroatom; optionally any two of R ⁇ R 11 vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
- the invention provides a process of silylating a composition comprising contacting silylation reactants with a complex of Formula (IV).
- the product of the silylation reaction is a hydrosilylated product, a dehydrogenative silylated product, or a combination thereof.
- the invention relates to cobalt complexes containing terpyridine ligands and their use as efficient hydrosilylation catalysts and/or dehydrogenative silylation and catalysts.
- a complex of the Formula (I) as illustrated above, wherein Co can be in any valence or oxidation state (e.g., +1, +2, or +3) for use in a hydrosilylation and/or dehydrogenative silylation and crosslinking reactions.
- a complex of Formula (IV) is provided for use in a hydrosilylation and/or dehydrogenative silylation.
- a class of cobalt terpyridine complexes has been found that are capable of hydrosilylation and/or dehydrogenative silylation reactions.
- the invention also addresses the advantage of reusing a single charge of catalyst for multiple batches of product, resulting in process efficiencies and lower costs.
- alkyl includes straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl, and cyclohexyl.
- substituted alkyl includes an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected.
- the substituent groups also do not substantially or deleterious ly interfere with the process.
- aryl refers to a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed.
- An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups.
- suitable aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.
- substituted aryl refers to an aromatic group substituted as set forth in the above definition of "substituted alkyl.” Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the attachment can be through a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. In one embodiment, the substituted aryl groups herein contain 1 to about 30 carbon atoms.
- alkenyl refers to any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group.
- suitable alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornyl, etc.
- alkynyl refers to any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carbon-carbon triple bond or elsewhere in the group.
- the term “unsaturated” refers to one or more double or triple bonds. In one embodiment, it refers to carbon-carbon double or triple bonds.
- the term “inert substituent” refers to a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The inert substituents also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of inert substituents include, but are not limited to, halo (fluoro, chloro, bromo,
- ether such as -OR wherein R is hydrocarbyl or substituted hydrocarbyl.
- hetero atoms refers to any of the Group 13-17 elements except carbon, and can include, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
- olefin refers to any aliphatic or aromatic hydrocarbon also containing one or more aliphatic carbon-carbon unsaturations. Such olefins may be linear, branched, or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substituents do not interfere substantially or deleteriously with the course of the desired reaction to produce the dehydrogenatively silylated or hydrosilylated product.
- the present invention provides, in one aspect, a cobalt complex, which complex can be used as a catalyst in hydrosilylation or dehydrogenative silylation reactions.
- the catalyst composition comprises a cobalt complex containing a terpyridine ligand and a chelating alkene-substituted silyl ligand coordinated to the cobalt, with the alkenyl substitution preferred at the beta-position relative to silicon.
- the catalyst is a complex of the Formula (I) or an adduct thereof:
- each occurrence of R - R is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent; optionally any two of R ! -R n vicinal to one another, R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a
- R 19 20 21 substituted or unsubstituted, saturated, or unsaturated cyclic structure; and Z is O, NR , or CR R , wherein R 19 , R 20 , and R 21 is independently hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a
- C6-C18 aryl a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, R , R , and R optionally contains at least one heteroatom.
- Co can be in any valence or oxidation state (e.g., +1, +2, or +3).
- R 12 and R 13 are independently chosen from a C1-C10 alkyl, or a C6-C18 aryl; Z is O; and R 14 -R 18 are hydrogen. In one embodiment, R 12 and R 13 are each methyl.
- R 12 and R 13 are each phenyl.
- the cobalt complex is a complex of the formula:
- the catalyst is generated by reacting a catalyst precursor prepared according to published procedure with the desired alkenyl-modified silane containing a SiH group in a solvent.
- Catalysts can be prepared by any suitable method now known to a person skilled in the field or later discovered.
- the catalysts can be prepared by reacting a terpyridine ligand with a metal complex such as Py 2 Co(CH 2 TMS) 2 in a solvent (such as pentane) with stirring at room temperature.
- the resulting complex may be treated with an ether to yield a mono complex, which can then be treated with the desired alkenyl-modified silane in a solvent (e.g., toluene).
- the cobalt catalysts with the terpyridine and alkene-mo dified silyl ligands exhibit good stability to air at atmospheric conditions.
- the present catalysts exhibit air stability that allows handling in the open atmosphere.
- Many iron or cobalt complexes known-previously to catalyze hydrosilylation or dehydrogenative silylation exhibit poor air stability rendering them impractical for industrial use.
- the present Terpy-Co complexes with the chelating alkene-mo dified silyl ligand have been found to overcome this major drawback.
- a terpyridine based cobalt complex with a single or mono ligand, L, coordinated to the cobalt is provided and which may also be used in a silylation process.
- the terpyridine cobalt mono-ligand complexes may have the empirical formula (Ci 5 RnN 3 )Co(L), where each occurrence of "R" and L is independently chosen from hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and "R,” other than hydrogen, optionally contain at least one heteroatom.
- the mono-ligand complex is a compound of the formula:
- R 1 - R 11 are independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, R ! -R n optionally containing one or more heteroatoms; optionally any two of R !
- R 4 -R 5 , and/or R 7 -R 8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
- R ⁇ -R 11 may be a phenyl, alkyl substituted phenyl, hydroxyphenyl, anilines, naphthalene, etc.
- a suitable substituted phenyl include phenyl groups comprising one or more CI -CIO alkyl substituents including, limited to, methyl, ethyl, propyl, isopropyl, butyl, etc.
- suitable alkyl phenyl groups include, but are not limited to tolyl, xylyl, naphthyl, etc.
- suitable substituted aryl groups include halo substituted aryl such as, for example, fluoro substituted aryl compounds.
- L is chosen from an alkyl trialkylsilyl group.
- the alkyl trialkylsilyl group has the formula -C(R ) 2 -Si(R ) 3 , and the complex is of the formula:
- R and R are independently hydrogen, a C 1 -C 18 alkyl, a C 1 -C 18
- R 22 23 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R and R optionally contain at least one heteroatom.
- suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc.
- suitable aryl groups include, but are not limited to, phenyl, alkyl substituted phenyl, hydroxyphenyl, anilines, naphthalene, etc.
- R ! -R n are each hydrogen.
- at least one of comprises an aryl group.
- at least one of R ! -R n comprises an aniline group.
- R 6 is advantageously fluorophenyl, dimethylaminophenyl, mesityl, or
- Non-limiting exam les of suitable compounds of Formula (IV) include:
- the complexes of Formula (IV) may be made reacting a terpyridine ligand with a metal complex such as Py 2 Co(CH 2 TMS) 2 in a solvent (such as pentane) with stirring at room temperature.
- a metal complex such as Py 2 Co(CH 2 TMS) 2
- a solvent such as pentane
- Py is an abbreviation for pyridine and TMS refers to the trimethylsilyl group.
- the resulting complex may be treated with an ether to yield a mono complex.
- complexes of Formula (IV) may be made by dissolving a terpyridine or terpyridine-based ligand in a solvent compatible with a (Py) 2 Co(CR' 2 SiR"3) 2 solution, where R' and R" are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.; combining the terpyridine solution and a (Py)2Co(CR'2SiR"3)2 solution cooled to between approximately 0 °C and -100 °C and stirring and fully evacuating, dissolving the residual and filtering; combining the filtered product with a solvent and stirring; and recrystallizing from a water insoluble liquid or mixture, at temperatures between approximately 0 °C and -100 °C.
- the catalyst is generated in-situ by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof.
- the catalysts can be unsupported or immobilized on a support material, for example, carbon, silica, alumina, MgCl 2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, poly(aminostyrene), or sulfonated polystyrene.
- the metal complexes can also be supported on dendrimers.
- exemplary functional groups include but are not limited to vinyl, SH, COOH, NH 2 or OH group.
- the cobalt catalysts of Formula (I) or Formula (IV) can be used as a catalyst for a hydrosilylation process or a dehydrogenative silylation process.
- Each process generally comprises reacting (a) a silyl hydride compound with (b) an unsaturated compound having at least one unsaturated functional group.
- the silyl hydride employed in the reactions is not particularly limited. It can be, for example, any compound chosen from hydrosilanes or hydrosiloxanes including those compounds of the formulas R 24 m SiH p X4_( m+p ) or M a M H b D c D H d T e T H f Q g , where each R 24 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group, X is alkoxy, acyloxy, or silazane, m is 0-3, p is 1-3, (with the proviso that silicon remains tetravalent), and M, D, T, and Q have their usual meaning in siloxane nomenclature.
- the subscripts a, b, c, d, e, f, and g are such that the molar mass of the siloxane-type reactant is between 100 and 100,000 Dalton. In one
- an "M” group represents a monofunctional group of formula R 25 3 SiOi /2 , a "D” group
- a difunctional group of formula R 2 Si0 2/2 represents a difunctional group of formula R 2 Si0 2/2
- a "T” group represents a trifunctional group of formula R 25 Si0 3/2
- a "Q” group represents a tetrafunctional group of formula Si0 4/2
- an "M H “ group represents HR 25 2 SiOi/ 2
- a "T H " represents HSi0 3 / 2
- a "D H " group represents R 25 HSi0 2 / 2 .
- R 25 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, C6-C14 aryl or substituted aryl, wherein R 25 optionally contains at least one heteroatom.
- R 24 is chosen from a CI -CIO alkyl.
- X is chosen from a CI -CIO alkoxy.
- the instant invention also provides hydrosilylation with hydridosiloxanes comprising carbosiloxane linkages (for example, Si-CH 2 -Si-0-SiH, Si-CH 2 -CH 2 -Si-0-SiH or Si- arylene-Si-O-SiH).
- Carbosiloxanes contain both the -Si-(hydrocarbylene)-Si- and -Si-O-Si- functionalities, where hydrocarbyl ene represents a substituted or unsubstituted, divalent alkylene, cycloalkylene or arylene group.
- the synthesis of carbosiloxanes is disclosed in U.S. Patent No. 7,259,220; U.S. Patent No. 7,326,761 and U.S. Patent No. 7,507,775 all of which are incorporated herein in their entirety by reference.
- carbosiloxane linkages is R 3 Si(CHR JU ) x SiOSi R J 2 (OSi R J 2 ) y OSi R 2 H, wherein each occurrence of R 30 is independently a monovalent alkyl, cycloalkyl or aryl group such as CI -CI 8 alkyl, CI -CI 8 substituted alkyl, C6-C14 aryl or substituted aryl.
- suitable groups include, for example, methyl, ethyl, cyclohexyl or phenyl.
- R 30 independently may also be H.
- the subscript x has a value of 1-8
- y has a value from zero to 10 and is preferably zero to 4.
- a specific example of a hydridocarbosiloxane is (CH3)3SiCH 2 CH 2 Si(CH3) 2 OSi(CH3) 2 H.
- Hydridocarbosilanes are another class useful for the hydrosilylation and
- Hydridocarbosilanes have SiH bonds as well as linkages such as -Si-(CH 2 ) X -Si- (wherein x is an integer greater than or equal to 1 , and is preferably 1 - 8) and other Si-hydrocarbylene groups in the molecular formula, but no siloxane linkages.
- hydrocarbylene refers to a substituted or unsubstituted divalent alkylene, cycloalkylene or arylene group. They can be linear, cyclic or branched and contain more than one SiH bond per molecule. The SiH bonds can be terminal or distributed internally along the Si-hydrocarbylene chains in the molecule.
- An exemplary formula for hydridocarbosilanes is
- R 3Si(CHR ) x Si R 2 H, R and x having the meanings defined above.
- Specific examples of hydridocarbosilanes are (CH 3 ) 3 SiCH 2 CH 2 Si(CH 3 ) 2 H, H(CH 3 ) 2 SiCH 2 CH 2 Si(CH 3 ) 2 H,
- dehydrogenative silylation enables the synthesis of saturated and unsaturated silahydrocarbons as illustrated in Example 15.
- the unsaturated compound containing an unsaturated functional group employed in the hydrosilylation reaction is generally not limited and can be chosen from an unsaturated compound as desired for a particular purpose or intended application.
- the unsaturated compound can be a mono-unsaturated compound or it can comprise two or more unsaturated functional groups. In one embodiment, the unsaturated group can comprise an aliphatically unsaturated functional group.
- the unsaturated compound can be a mono-unsaturated compound or it can comprise two or more unsaturated functional groups. In one embodiment, the unsaturated group can be an aliphatically unsaturated functional group.
- suitable compounds containing an unsaturated group include, but are not limited to, unsaturated polyethers such as alkyl-capped allyl polyethers, vinyl functionalized alkyl capped allyl or methylallyl polyethers; terminally unsaturated amines; alkynes; C2-C45 olefins, in one embodiment alpha olefins; unsaturated epoxides such as allyl glycidyl ether and vinyl cyclohexene-oxide; terminally unsaturated acrylates or methyl acrylates; unsaturated aryl ethers; unsaturated aromatic hydrocarbons; unsaturated cycloalkanes such as trivinyl cyclohexane; vinyl-functionalized polymer or oligomer; and vinyl- functionalized and/or terminally-unsaturated alkenyl-silanes and/or silicones; unsaturated fatty acids; unsaturated fatty esters; or combinations of two or more thereof.
- unsaturated substrates include, but are not limited to, ethylene, propylene, isobutylene, 1-hexene, 1-octene, 1-octadecene, styrene, alpha-methylstyrene, cyclopentene, norbornene, 1,5-hexadiene, norbomadiene, vinylcyclohexene, allyl alcohol, allyl-terminated polyethyleneglycol, allylacrylate, allyl methacrylate, allyl glycidyl ether, allyl-terminated isocyanate-or acrylate prepolymers, polybutadiene, allylamine, methallyl amine, acetylene, phenylacetylene, vinyl- pendent or vinyl-terminal polysiloxanes, vinylcyclosiloxanes, vinylsiloxane resins, vinyl-functional synthetic or natural minerals, etc.
- Unsaturated polyethers suitable for the hydrosilylation reaction include
- R 27 0(CHR 28 CH 2 0) w (CH 2 CH 2 0) z — CR 29 2— C ⁇ C— CR 29 2 (OCH 2 CH 2 ) z (OCH 2 CHR 28 ) w R 27 wherein R 26 denotes an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methylallyl, propargyl or 3-pentynyl.
- R 26 denotes an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methylallyl, propargyl or 3-pentynyl.
- the unsaturation is olefmic, it is desirably terminal to facilitate smooth hydrosilylation.
- the unsaturation is a triple bond, it may be internal.
- R 27 is independently hydrogen, vinyl, allyl, methallyl, or a polyether capping group of from 1 to 8 carbon atoms such as the alkyl groups: CH 3 , n-C 4 H , t-C 4 t3 ⁇ 4 or i-CsHn, the acyl groups such as CH 3 COO, t-C 4 H COO, the beta-ketoester group such as CH 3 C(0)CH 2 C(0)0, or a
- R and R are monovalent hydrocarbon groups such as the C1-C20 alkyl groups, for example, methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, or the aryl groups, for example, phenyl and naphthyl, or the alkaryl groups, for example, benzyl, phenylethyl and nonylphenyl, or the cycloalkyl groups, for example, cyclohexyl and cyclooctyl.
- R29 may also be
- Methyl is particularly suitable for the R and R groups.
- Each occurrence of z is 0 to 100 inclusive and each occurrence of w is 0 to 100 inclusive. In one embodiment, the values of z and w are 1 to 50 inclusive.
- the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof.
- the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof.
- the silylated product from the process comprises a
- the silylated product from the process comprises a dehydrogenative silylated product. In one embodiment, the product comprises a mixture of hydrosilylated and dehydrogenative silylated product.
- the silylhydride can be added to a mixture containing the metal complex and the unsaturated olefin.
- the unsaturated olefin can be added to a mixture containing the metal complex and the silylhydride.
- a mixture of silylhydride and unsaturated olefin can be added to a mixture of metal complex, silylhydride and unsaturated olefin.
- Effective catalyst usage for silylation ranges from 0.001 mole percent to 10 mole percent based on the molar quantity of the alkene to be reacted. Preferred levels are from 0.005 to 1 mole percent. Reaction may be run at temperatures from about -10°C up to 300°C, depending on the thermal stability of the alkene, silyl hydride and the specific pyridine di-imine complex.
- the catalyst composition can be provided for either the dehydrogenative silylation or hydrosilylation reactions in an amount sufficient to provide a desired metal concentration.
- the concentration of the catalyst is about 5% (50000 ppm) or less based on the total weight of the reaction mixture; about 1% (10000 ppm) or less; 5000 ppm or less based on the total weight of the reaction mixture; about 1000 ppm or less; about 500 ppm or less based on the total weight of the reaction mixture; about 100 ppm or less; about 50 ppm or less based on the total weight of the reaction mixture; even about 10 ppm or less based on the total weight of the reaction mixture.
- the concentration of the catalyst is from about 10 ppm to about 50000 ppm; about 100 ppm to about 10000 ppm; about 250 ppm to about 5000 ppm; even about 500 ppm to about 2500 ppm.
- the concentration of the metal atom is from about 100 to about 1000 ppm based on the total weight of the reaction mixture.
- the concentration of the metal e.g., cobalt
- numerical values can be combined to form new and non- disclosed ranges.
- the silylation reactions of this invention can be run at subatmospheric and supra- atmospheric pressures. Typically, pressures from about 1 atmosphere (0.1 MPa) to about 200 atmospheres (20 MPa), preferably to about 50 atmospheres (5.0 MPa), are suitable. Higher pressures are effective with volatile and/or less reactive alkenes which require confinement to enable high conversions.
- the catalysts are useful for dehydrogenative silylation of a composition containing a silyl hydride and a compound having at least one unsaturated group.
- the process includes contacting the composition with a suitable metal complex, either supported or unsupported, to cause the silyl hydride to react with the compound having at least one unsaturated group to produce a dehydrogenative silylation product, which may contain the metal complex catalyst.
- the dehydrogenative silylation reaction can be conducted optionally in the presence of a solvent. If desired, when the dehydrogenative silylation reaction is completed, the metal complex can be removed from the reaction product by magnetic separation and/or filtration. These reactions may be performed neat, or diluted in an appropriate solvent. Typical solvents include benzene, toluene, diethyl ether, etc. It is preferred that the reaction is performed under an inert atmosphere.
- a singly-unsaturated olefin may be used to crosslink silyl-hydride containing polymers.
- a silyl-hydride polysiloxane such as Momentive SL6020 Dl (MDisD H 3 oM)
- MMID H 3 oM Momentive SL6020 Dl
- a variety of new materials can be produced by this method by varying the hydride polymer and length of the olefin used for the crosslinking.
- the catalysts used in the process of the invention have utility in the preparation of useful silicone products, including, but not limited to, coatings, for example release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and silicone surfactants for stabilizing polyurethane foams.
- coatings for example release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and silicone surfactants for stabilizing polyurethane foams.
- the cobalt complexes disclosed herein can be used as a catalyst for various reactions including, for example, the hydrosilylation of a composition containing a silyl hydride and a compound having at least one aliphatically unsaturated group.
- the hydrosilylation process includes contacting the composition with a cobalt complex of the Formula (I), either supported or unsupported, to cause the silyl hydride to react with the compound having at least one aliphatically unsaturated group to produce a hydrosilylation product.
- the hydrosilylation product may contain the components from the catalyst composition.
- the hydrosilylation reaction can be conducted optionally in the presence of a solvent, at subatmospheric or supra-atmospheric pressures and in batch or continuous processes.
- the hydrosilylation reaction can be conducted at temperatures of from about -10 °C to about 200 °C. If desired, when the hydrosilylation reaction is completed, the catalyst composition can be removed from the reaction product by filtration.
- reaction of a silyl hydride with an unsaturated compound can provide a mixture of hydrosilylated and dehydrogenatively silylated products. In one embodiment, a majority of the products is the hydrosilylated product.
- the cobalt complexes of the invention are, in embodiments, efficient and selective in catalyzing hydrosilylation reactions.
- the metal complexes of the invention are employed in the hydrosilylation of a silyl hydride and a compound containing an unsaturated group, the reaction products are essentially free of unreacted unsaturated compound and/or any combination thereof.
- the reaction products do not contain the unreacted and its isomerization products.
- "essentially free” is meant no more than 10 wt. %, no more than 5 wt. %, no more than 3 wt. %; even no more than 1 wt. % based on the total weight of the hydrosilylation product.
- "Essentially free of internal addition products” is meant that silicon is added to the terminal carbon.
- Benzene -de was purchased from Cambridge Isotope Laboratories, dried over sodium and stored with 4 A molecular sieves in the dry box.
- the 2,2';6'2"-terpyridine (terpy) ligand was obtained from Strem, dried under high vacuum overnight and brought into the dry box.
- Liquid substrates were dried over LiAlH 4 or CaH 2 and degased under high vacuum before use.
- NMR spectra were acquired on a Varian INOVA-500 or Bruker-500 MHz spectrometer. The chemical shifts ( ⁇ ) of 1H NMR spectra are given in parts per million and referenced to the solvent residual of benzene -de (7.16 ppm).
- chlorodiphenylsilane (1 1 g, 50 mmol) was added dropwise to the solution. Large quantities of a fluffy white precipitate (Et 3 NHCl) were observed immediately. The mixture was warmed to room temperature and stirred for 1 h. The resulting solution was filtered through Celite and washed with Et 2 0. The filtrate was concentrated and yielded a colorless oil, which upon distillation (84 - 85 °C, 65 mmTorr) afforded the desired product as a colorless oil in 80% yield.
- Alloxydimethylsilane was prepared in a manner similar to alloxydiphenylsilane.
- a solution of allyl alcohol (2.9 g, 50 mmol) and triethylamine (5.1 g, 50 mmol) in Et 2 0 (250 mL) was cooled in an ice bath. While rapid stirring, the solution was added with chlorodimethylsilane (4.7 g, 50 mmol) dropwise. Large quantities of a fluffy white precipitate (Et 3 NHCl) were observed immediately. The mixture was warmed to room temperature and stirred for 1 hour. The resulting solution was filtered through Celite and washed with Et 2 0.
- This compound was prepared in a manner similar to (terpy)Co(Ph 2 SiOC 3 H 5 ).
- pentane 1 mL
- alloxydimethylsilane 16 mg, 0.12 mmol
- the solid was isolated through filtration and purified by dissolving in toluene and passing through Celite.
- the resulting solution was layered with pentane and stored at -35 °C for 1 day and yielded purple crystals identified as the desired product.
- n-Octyltriethoxysilane (Product A), is the anti-Markovnikov hydrosilylation product.
- 2-Triethoxysilyloctane (Product B), is the
- Product C is the allylic silane (2-Octenyltriethoxysilane) produced via dehydrogenative silylation. Octane was formed in equimolar amounts with Product C.
- Example 6 Hydrosilylation of 1-octene with triethoxysilane using (terpy ⁇ ofPh ⁇ SiOC ⁇ HQ in the glove box
- Example 7 Hydrosilylation of 1-octene with triethoxysilane using (terpy Co(Me7SiOC3HQ in the glove box
- Example 8 Bench-top hydrosilylation of 1-octene with triethoxysilane using
- a scintillation vial was charged with a suspension of 0.154 g (0.319 mmol) (4-NMe 2 -Ph-Terpy)CoCl 2 in approximately 10 mL of diethyl ether. The mixture was chilled at -35 °C for 10 minutes. With vigorous stirring, a diethyl ether solution of (trimethylsilyl)methyllithium (0.060 g, 0.639 mmol in 2 mL diethyl ether) was added dropwise to the chilled suspension.
- a scintillation vial was charged with a stir bar, 0.112 g (1 mmol) of 1-octene and 0.116 g (1 mmol) of triethylsilane. (Terpy)CoCH 2 TMS (0.002 g, 0.5 mol%) was then added into the reaction mixture as a solid.
- the vial was sealed with a cap and stirred at 23 °C for 1 hour, after which the reaction was quenched by exposure to air.
- the product mixture was filtered through silica gel and eluted with hexane. The resulting solution was dried
- Example 14 Silylation of 1 -octene with l-(2-trimethylsilylethyl)-l,l,3,3,-tetramethyldisiloxane
- Examples 16 - 20 Silylation of Vinylcyclohexene oxide (3-vinyl-7-oxabicvclor4.1.01heptane) with MD H M with various TerpyCoNs Catalysts
- Example 16 the unsubstituted ligand was used, in Example 17, the 4-fluorophenyl, in Example 18, the 4- dimethylaminophenyl, in Example 19, the 4-mesityl and in Example 20, the 4-(pyrrolidin-l-yl).
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Abstract
Disclosed herein are cobalt terpyridine complexes containing a single ligand coordinated to the cobalt, and their use as hydrosilylation and/or dehydrogenative silylation and crosslinking catalysts. The cobalt complexes also exhibit adequate air stability for handling and manipulation.
Description
COBALT CATALYSTS AND THEIR USE
FOR HYDROSILYLATION AND DEHYDROGENATIVE SILYLATION
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U. S. Provisional Application No. 61/906,204, filed on November 19, 2013 entitled "Cobalt Catalysts and Their Use for Hydrosilylation and Dehydrogenative Silylation" and U.S. Provisional Application No. 62/031 ,463 filed on July 31 , 2014 entitled "Terpyridine Cobalt Complexes and Their Use as Catalysts," the entire disclosures of which are incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
[0002] This invention relates generally to transition metal-containing compounds, more specifically to cobalt complexes containing terpyridine ligands and their use as catalysts for hydrosilylation and dehydrogenative silylation reactions.
BACKGROUND OF THE INVENTION
[0003] Hydrosilylation chemistry, typically involving a reaction between a silyl hydride and an unsaturated organic group, is the basis for synthetic routes to produce commercial silicone -based products like silicone surfactants, silicone fluids and silanes as well as many addition cured products like sealants, adhesives, and coatings. Typical hydrosilylation reactions use precious metal catalysts to catalyze the addition of a silyl-hydride (Si-H) to an unsaturated group, such as an olefin. In these reactions, the resulting product is a silyl-substituted, saturated compound. In most of these cases, the addition of the silyl group proceeds in an anti-Markovnikov manner, i.e., to the less substituted carbon atom of the unsaturated group. Most precious metal catalyzed
hydrosilylations only work well with terminally unsaturated olefins, as internal unsaturations are generally non-reactive or only poorly reactive. There are currently only limited commercially viable methods for the general silylation of olefins where after the addition of the Si-H group there still remains an unsaturation in the original substrate. This reaction, termed a dehydrogenative silylation, has potential uses in the synthesis of new silicone materials, such as silanes, silicone fluids, crosslinked silicone elastomers, and silylated or silicone-crosslinked organic polymers such as polyolefms, unsaturated polyesters, and the like.
[0004] Various precious metal complex catalysts are known in the art including a platinum complex containing unsaturated siloxanes as ligands, which is known in the art as Karstedt's
catalyst. Other platinum-based hydrosilylation catalysts include Ashby's catalyst, Lamoreaux's catalyst, and Speier's catalyst.
[0005] Other metal-based catalysts have been explored including, for example, rhodium complexes, iridium complexes, palladium complexes and even first-row transition metal-based catalysts to promote limited hydrosilylations and dehydrogenative silylations.
[0006] U.S. Patent No. 5,955,555 discloses the synthesis of certain iron or cobalt pyridine di-imine (PDI) complexes bearing two anionic ligands. The preferred anions are chloride, bromide, and tetrafluoroborate. U.S. Patent No. 7,442,819 discloses iron and cobalt complexes of certain tricyclic ligands containing a "pyridine" ring substituted with two imino groups. U.S. Patent Nos. 6,461,994, 6,657,026 and 7,148,304 disclose several catalyst systems containing certain transitional metal-PDI complexes. U.S. Patent No. 7,053,020 discloses a catalyst system containing, inter alia, one or more bisarylimino pyridine iron or cobalt catalyst. Chirik et al describe bisarylimino pyridine cobalt complexes with anionic ligands (Inorg. Chem. 2010, 49, 6110 and JACS. 2010, 132, 1676.) However, the catalysts and catalyst systems disclosed in these references are described for use in the context of olefin hydrogenation, polymerizations and/or oligomerisations, not in the context of dehydrogenative silylation reactions. U.S. Patent No. 8,236,915 discloses hydrosilylation using Mn, Fe, Co, and Ni catalysts containing pyridinediimine ligands. However, these catalysts are sensitive to air and must be handled in a glove box.
[0007] There is a continuing need in the silylation industry for non-precious metal-based catalysts that are effective for efficiently and selectively catalyzing hydrosilylation and/or dehydrogenative silylations. There is also a need for metal-based catalysts that are air stable. Many metal-based catalysts, including those based on iron or cobalt, are not stable under atmospheric conditions. This makes such materials generally unsuitable for application on a production or industrial scale.
[0008] Further, many industrially important homogeneous metal catalysts suffer from the drawback that following consumption of the first charge of substrates, the catalytically active metal is lost to aggregation and agglomeration and its beneficial catalytic properties are substantially diminished via colloid formation or precipitation. This is a costly loss, especially for noble metals such as Pt. Heterogeneous catalysts are used to alleviate this problem but have limited use for polymers and also have lower activity than homogeneous counterparts. For example, the two primary homogeneous catalysts for hydrosilylation, Speier's and Karstedt's, often lose activity after catalyzing a charge of olefin and silyl- or siloxyhydride reaction. If a single charge of the
homogeneous catalyst could be re -used for multiple charges of substrates, then catalyst and process cost advantages would be significant.
SUMMARY OF THE INVENTION
[0009] In one aspect, the present invention provides a complex of the Formula:
wherein each occurrence of R1- R11 is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R^R11, other than hydrogen, optionally contain at least one heteroatom; optionally any two of R!-Rn vicinal to one another, R4- R5, and/or R7-R8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, or an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
[0010] In one embodiment, R!-Rn are hydrogen.
[0011] In one embodiment, L is -C(R22)2-Si(R23)3 where R22 and R23 are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
[0012] In one embodiment, wherein R!-Rn are hydrogen.
[0013] In one embodiment, the catal st is of the formula:
CH2Si(CH3)3
[0014] In one embodiment, at least one of R -R is chosen from an aryl group or a substituted aryl group. In one embodiment, the substituted aryl group is chosen from tolyl, xylyl, naphthyl, mesityl, aniline, fluorophenyl, or a combination of two or more thereof.
[0015] In one embodiment, R!-R5 and R7-Rn are hydrogen, and R6 is chosen from pyrrolidino, flourophenyl, aniline, or mesityl.
[0016] In one embodiment, the complex is of the formula:
CH2Si(CH3)3
[0017] In one aspect, the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof:
1 18
wherein each occurrence of R - R is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a
substituted C6-C18 aryl, or an inert substituent wherein one or more of R^-R11, other than hydrogen, optionally contain at least one heteroatom; optionally any two of R!-Rn vicinal to one another, R4- R5, and/or R7-R8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, or an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
[0018] In one embodiment, R!-Rn are hydrogen.
[0019] In one embodiment, L is -C(R22)2-Si(R23)3 where R22 and R23 are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
[0020] In one embodiment, R!-Rn are hydrogen.
[0021] In one embodiment, the catal st is of the formula:
[0022] In one embodiment, at least one of R!-Rn is chosen from an aryl group or a substituted aryl group.
[0023] In one embodiment, the substituted aryl group is aniline.
[0024] In one embodiment, the complex is of the formula:
CH2Si(CH3)3
[0025] In one embodiment, the process comprises removing the complex and/or derivatives thereof from the silylated product.
[0026] In one embodiment, the silylated product comprises a hydrosilylation product.
[0027] In one embodiment, the silylated product comprises a dehydrogenatively silylated product.
[0028] In one embodiment, the silylated product comprises a mixture of (i) a hydrosilylation product, and (ii) a dehydrogenative silylated product.
[0029] In one embodiment, the unsaturated compound (a) is chosen from a linear or branched olefin; a cycloalkene; an alkyl-capped allyl polyether; a vinyl-functional alkyl-capped allyl or methallyl polyether; an alkyl-capped terminally unsaturated amine; an alkyne; a terminally unsaturated acrylate or methacrylate; an unsaturated aryl ether; a vinyl-functionalized polymer or oligomer; a vinyl-functionalized and/or terminally-unsaturated alkenyl-functional silane; and/or silicone; an unsaturated fatty acid; an unsaturated ester; or combinations of two or more thereof.
[0030] In one embodiment, the reaction is conducted under an inert atmosphere.
[0031] In one embodiment, the reaction is carried out at a temperature of -10°C to 300°C.
[0032] In one embodiment, the silyl hydride comprises a hydride fluid chosen from one or a combination of compounds of the formulas:
R24 mS iHpX4_(m+p) ;
MaMH bDcDH dTeTH fQg;
R30 3Si(CHR30)xSiOSi R30 2(OSi R30 2)yOSi R30 2H,
R30 3Si(CHR30)xSi R30 2H
24
where each R is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group; X is halogen, alkoxy, acyloxy, or silazane; m is 0-3; p is 1-3, with the proviso that the
25 tetrvalency of silicon is preserved; M represents a monofunctional group of formula R 3SiOi/2; a D
25
represents a difunctional group of formula R 2Si02/2; a T represents a trifunctional group of formula R25Si03/2; Q represents a tetrafunctional group of formula Si04/2; MH represents
25 H H 25 25
HR 2SiOi/2, T represents HSi03/2, and D group represents R HSi02/2; each occurrence of R is independently a Ci-Cig alkyl, a Ci-Cig substituted alkyl, a C6-C14 aryl or substituted aryl, wherein
25
R optionally contains at least one heteroatom; subscripts a, b, c, d, e, f, and g are such that the
30 molar mass of the compound is between 100 and 100,000 Dalton; each occurrence of R is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C14 aryl or substituted aryl; x is 1- 8, and y is 0-10.
[0033] In one embodiment, the complex is immobilized on a support. In one embodiment, the support is chosen from carbon, silica, alumina, MgCl2, zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.
[0034] In one aspect, the present invention provides a composition produced by the process of claim 10, wherein the composition contains the catalyst or derivatives thereof. In one
embodiment, the composition comprises at least one component selected from the group of silanes, silicone fluids, and crosslinked silicones, or a combination of two or more thereof.
[0035] In one aspect, the invention provides a complex of Formula (IV)
wherein each occurrence of R1- R11 is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R^R11, other than hydrogen, optionally contain at least one heteroatom; optionally any two of R^R11 vicinal to one another, R4-R5, and/or R7-R8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
[0036] In another aspect, the invention provides a process of silylating a composition comprising contacting silylation reactants with a complex of Formula (IV). In one embodiment, the product of the silylation reaction is a hydrosilylated product, a dehydrogenative silylated product, or a combination thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0037] The invention relates to cobalt complexes containing terpyridine ligands and their use as efficient hydrosilylation catalysts and/or dehydrogenative silylation and catalysts. In one embodiment of the invention, there is provided a complex of the Formula (I), as illustrated above,
wherein Co can be in any valence or oxidation state (e.g., +1, +2, or +3) for use in a hydrosilylation and/or dehydrogenative silylation and crosslinking reactions. In one embodiment, a complex of Formula (IV) is provided for use in a hydrosilylation and/or dehydrogenative silylation. In particular, according to one embodiment of the invention, a class of cobalt terpyridine complexes has been found that are capable of hydrosilylation and/or dehydrogenative silylation reactions. The invention also addresses the advantage of reusing a single charge of catalyst for multiple batches of product, resulting in process efficiencies and lower costs.
[0038] As used herein, the term "alkyl" includes straight, branched and cyclic alkyl groups. Specific and non-limiting examples of alkyls include, but are not limited to, methyl, ethyl, propyl, isobutyl, and cyclohexyl.
[0039] As used herein, the term "substituted alkyl" includes an alkyl group that contains one or more substituent groups that are inert under the process conditions to which the compound containing these groups is subjected. The substituent groups also do not substantially or deleterious ly interfere with the process.
[0040] As used herein, the term "aryl" refers to a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. An aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups. Examples of suitable aryls include, but are not limited to, tolyl, xylyl, phenyl and naphthalenyl.
[0041] As used herein, the term "substituted aryl" refers to an aromatic group substituted as set forth in the above definition of "substituted alkyl." Similar to an aryl, a substituted aryl may have one or more aromatic rings, which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the attachment can be through a heteroatom (such as nitrogen) of the heteroaromatic ring instead of a carbon. In one embodiment, the substituted aryl groups herein contain 1 to about 30 carbon atoms.
[0042] As used herein, the term "alkenyl" refers to any straight, branched, or cyclic alkenyl group containing one or more carbon-carbon double bonds, where the point of substitution can be either a carbon-carbon double bond or elsewhere in the group. Examples of suitable alkenyls include, but are not limited to, vinyl, propenyl, allyl, methallyl, ethylidenyl norbornyl, etc.
[0043] As used herein, the term "alkynyl" refers to any straight, branched, or cyclic alkynyl group containing one or more carbon-carbon triple bonds, where the point of substitution can be either at a carbon-carbon triple bond or elsewhere in the group.
[0044] As used herein, the term "unsaturated" refers to one or more double or triple bonds. In one embodiment, it refers to carbon-carbon double or triple bonds.
[0045] As used herein, the term "inert substituent" refers to a group other than hydrocarbyl or substituted hydrocarbyl, which is inert under the process conditions to which the compound containing the group is subjected. The inert substituents also do not substantially or deleteriously interfere with any process described herein that the compound in which they are present may take part in. Examples of inert substituents include, but are not limited to, halo (fluoro, chloro, bromo,
30 30
and iodo), and ether such as -OR wherein R is hydrocarbyl or substituted hydrocarbyl.
[0046] As used herein, the term "hetero atoms" refers to any of the Group 13-17 elements except carbon, and can include, for example, oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.
[0047] As used herein, the term "olefin" refers to any aliphatic or aromatic hydrocarbon also containing one or more aliphatic carbon-carbon unsaturations. Such olefins may be linear, branched, or cyclic and may be substituted with heteroatoms as described above, with the proviso that the substituents do not interfere substantially or deleteriously with the course of the desired reaction to produce the dehydrogenatively silylated or hydrosilylated product.
Cobalt Complexes
[0048] The present invention provides, in one aspect, a cobalt complex, which complex can be used as a catalyst in hydrosilylation or dehydrogenative silylation reactions. In one embodiment, the catalyst composition comprises a cobalt complex containing a terpyridine ligand and a chelating alkene-substituted silyl ligand coordinated to the cobalt, with the alkenyl substitution preferred at the beta-position relative to silicon. In one embodiment, the catalyst is a complex of the Formula (I) or an adduct thereof:
19 20 21 substituted or unsubstituted, saturated, or unsaturated cyclic structure; and Z is O, NR , or CR R , wherein R 19 , R 20 , and R 21 is independently hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a
19 20 21
C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, R , R , and R optionally contains at least one heteroatom. In the catalyst complex Co can be in any valence or oxidation state (e.g., +1, +2, or +3).
[0049] In one embodiment, R 12 and R 13 are independently chosen from a C1-C10 alkyl, or a C6-C18 aryl; Z is O; and R14-R18 are hydrogen. In one embodiment, R12 and R13 are each methyl.
In still another embodiment, R 12 and R 13 are each phenyl.
[0050] In one embodiment, the cobalt complex is a complex of the formula:
[0052] The cobalt catalysts with the terpyridine and alkene-mo dified silyl ligands exhibit good stability to air at atmospheric conditions. The present catalysts exhibit air stability that allows handling in the open atmosphere. Many iron or cobalt complexes known-previously to catalyze hydrosilylation or dehydrogenative silylation exhibit poor air stability rendering them impractical for industrial use. The present Terpy-Co complexes with the chelating alkene-mo dified silyl ligand, however, have been found to overcome this major drawback.
[0053] In another aspect, a terpyridine based cobalt complex with a single or mono ligand, L, coordinated to the cobalt is provided and which may also be used in a silylation process. The terpyridine cobalt mono-ligand complexes may have the empirical formula (Ci5RnN3)Co(L), where each occurrence of "R" and L is independently chosen from hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and "R," other than hydrogen, optionally contain at least one heteroatom.
[0054] In one embodiment, the mono-ligand complex is a compound of the formula:
where R1- R11 are independently hydrogen, a C1-C18 alkyl, a C1-C18 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, R!-Rn optionally containing one or more heteroatoms; optionally any two of R!-Rn vicinal to one another, R4-R5, and/or R7-R8 taken together may form a ring being a substituted or
unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom. In one embodiment, one or more of R^-R11 may be a phenyl, alkyl substituted phenyl, hydroxyphenyl, anilines, naphthalene, etc. Non-limiting examples of a suitable substituted phenyl include phenyl groups comprising one or more CI -CIO alkyl substituents including, limited to, methyl, ethyl, propyl, isopropyl, butyl, etc. Examples of suitable alkyl phenyl groups include, but are not limited to tolyl, xylyl, naphthyl, etc. Still other examples of suitable substituted aryl groups include halo substituted aryl such as, for example, fluoro substituted aryl compounds. In another embodiment, may be chosen from a heterocyclic compound. Examples of suitable heterocyclic compounds include, but are not limited to, nitrogen-containing rings. A non-limiting example of suitable heterocyclic group is the pyrrolidino group.
[0055] In one embodiment, L is chosen from an alkyl trialkylsilyl group. In one
22 23
embodiment, the alkyl trialkylsilyl group has the formula -C(R )2-Si(R )3, and the complex is of the formula:
where each occurrence of R and R are independently hydrogen, a C 1 -C 18 alkyl, a C 1 -C 18
22 23 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R and R optionally contain at least one heteroatom. Examples of suitable alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, pentyl, etc. Examples of suitable aryl groups include, but are not limited to, phenyl, alkyl substituted phenyl, hydroxyphenyl, anilines, naphthalene, etc. In one embodiment, R!-Rn are each hydrogen. In one embodiment, at least one of comprises an aryl group. In one embodiment, at least one of R!-Rn comprises an aniline group. In one embodiment, R6 is advantageously fluorophenyl, dimethylaminophenyl, mesityl, or
22 23
the pyrrolidino group. The -C(R )2-Si(R )3 group may also be referred to as a neosilyl group and may be abbreviated "Ns".
[0056] Non-limiting exam les of suitable compounds of Formula (IV) include:
[0057] Various methods can be used to prepare the catalyst utilized in the process of the present invention. The complexes of Formula (IV) may be made reacting a terpyridine ligand with a metal complex such as Py2Co(CH2TMS)2 in a solvent (such as pentane) with stirring at room temperature. Py is an abbreviation for pyridine and TMS refers to the trimethylsilyl group. The resulting complex may be treated with an ether to yield a mono complex. In one embodiment, complexes of Formula (IV) may be made by dissolving a terpyridine or terpyridine-based ligand in a solvent compatible with a (Py)2Co(CR'2SiR"3)2 solution, where R' and R" are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.; combining the terpyridine solution and a (Py)2Co(CR'2SiR"3)2 solution cooled to between approximately 0 °C and -100 °C and stirring and fully evacuating, dissolving the residual and filtering; combining the filtered product with a solvent and stirring; and recrystallizing from a water insoluble liquid or mixture, at temperatures between approximately 0 °C and -100 °C. In one embodiment, the catalyst is generated in-situ by contacting a catalyst precursor with an activator in the presence of a liquid medium containing at least one component selected from the group consisting of a solvent, the silyl hydride, the compound containing at least one unsaturated group, and combinations thereof.
[0058] In the silylation reaction processes, the catalysts can be unsupported or immobilized on a support material, for example, carbon, silica, alumina, MgCl2 or zirconia, or on a polymer or prepolymer, for example polyethylene, polypropylene, polystyrene, poly(aminostyrene), or sulfonated polystyrene. The metal complexes can also be supported on dendrimers. In some embodiments, for the purposes of attaching the metal complexes of the invention to a support, it is desirable that at least one of R1 to R11 of the metal complexes, has a functional group that is effective to covalently bond to the support. Exemplary functional groups include but are not limited to vinyl, SH, COOH, NH2 or OH group.
Catalyzed Reactions
[0059] In accordance with the present invention, the cobalt catalysts of Formula (I) or Formula (IV) can be used as a catalyst for a hydrosilylation process or a dehydrogenative silylation process. Each process generally comprises reacting (a) a silyl hydride compound with (b) an unsaturated compound having at least one unsaturated functional group.
[0060] The silyl hydride employed in the reactions is not particularly limited. It can be, for example, any compound chosen from hydrosilanes or hydrosiloxanes including those compounds of the formulas R24 mSiHpX4_(m+p) or MaMH bDcDH dTeTH fQg, where each R24 is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group, X is alkoxy, acyloxy, or silazane, m is 0-3, p is 1-3, (with the proviso that silicon remains tetravalent), and M, D, T, and Q have their usual meaning in siloxane nomenclature. The subscripts a, b, c, d, e, f, and g are such that the molar mass of the siloxane-type reactant is between 100 and 100,000 Dalton. In one
embodiment, an "M" group represents a monofunctional group of formula R 253SiOi/2, a "D" group
25
represents a difunctional group of formula R 2Si02/2, a "T" group represents a trifunctional group of formula R25Si03/2, and a "Q" group represents a tetrafunctional group of formula Si04/2, an "MH" group represents HR25 2SiOi/2, a "TH" represents HSi03/2, and a "DH" group represents R25HSi02/2.
Each occurrence of R 25 is independently CI -CI 8 alkyl, CI -CI 8 substituted alkyl, C6-C14 aryl or substituted aryl, wherein R 25 optionally contains at least one heteroatom. In one embodiment, R 24 is chosen from a CI -CIO alkyl. In one embodiment, X is chosen from a CI -CIO alkoxy.
[0061] The instant invention also provides hydrosilylation with hydridosiloxanes comprising carbosiloxane linkages (for example, Si-CH2-Si-0-SiH, Si-CH2-CH2-Si-0-SiH or Si- arylene-Si-O-SiH). Carbosiloxanes contain both the -Si-(hydrocarbylene)-Si- and -Si-O-Si- functionalities, where hydrocarbyl ene represents a substituted or unsubstituted, divalent alkylene, cycloalkylene or arylene group. The synthesis of carbosiloxanes is disclosed in U.S. Patent No.
7,259,220; U.S. Patent No. 7,326,761 and U.S. Patent No. 7,507,775 all of which are incorporated herein in their entirety by reference. An exemplary formula for hydridosiloxanes with
30 30 30 30 30
carbosiloxane linkages is R 3Si(CHRJU)xSiOSi RJ 2(OSi RJ 2)yOSi R 2H, wherein each occurrence of R 30 is independently a monovalent alkyl, cycloalkyl or aryl group such as CI -CI 8 alkyl, CI -CI 8 substituted alkyl, C6-C14 aryl or substituted aryl. Non- limiting examples of suitable groups include, for example, methyl, ethyl, cyclohexyl or phenyl. Additionally, R 30 independently may also be H. The subscript x has a value of 1-8, y has a value from zero to 10 and is preferably zero to 4. A specific example of a hydridocarbosiloxane is (CH3)3SiCH2CH2Si(CH3)2OSi(CH3)2H.
[0062] Hydridocarbosilanes are another class useful for the hydrosilylation and
dehydrogenative silylation reactions of the instant invention. Hydridocarbosilanes have SiH bonds as well as linkages such as -Si-(CH2)X-Si- (wherein x is an integer greater than or equal to 1 , and is preferably 1 - 8) and other Si-hydrocarbylene groups in the molecular formula, but no siloxane linkages. As defined above, hydrocarbylene refers to a substituted or unsubstituted divalent alkylene, cycloalkylene or arylene group. They can be linear, cyclic or branched and contain more than one SiH bond per molecule. The SiH bonds can be terminal or distributed internally along the Si-hydrocarbylene chains in the molecule. An exemplary formula for hydridocarbosilanes is
30 30 30 30
R 3Si(CHR )xSi R 2H, R and x having the meanings defined above. Specific examples of hydridocarbosilanes are (CH3)3SiCH2CH2Si(CH3)2H, H(CH3)2SiCH2CH2Si(CH3)2H,
(CH3)3SiC6H4Si(CH3)2H, (CH3)3SiC6HioSi(CH3)2H, wherein -C6H4- is the phenylene linkage and - C6Hio- is the cyclohexylene linkage. Use of hydridocarbosilanes in hydrosilylation and
dehydrogenative silylation enables the synthesis of saturated and unsaturated silahydrocarbons as illustrated in Example 15.
[0063] The unsaturated compound containing an unsaturated functional group employed in the hydrosilylation reaction is generally not limited and can be chosen from an unsaturated compound as desired for a particular purpose or intended application. The unsaturated compound can be a mono-unsaturated compound or it can comprise two or more unsaturated functional groups. In one embodiment, the unsaturated group can comprise an aliphatically unsaturated functional group. The unsaturated compound can be a mono-unsaturated compound or it can comprise two or more unsaturated functional groups. In one embodiment, the unsaturated group can be an aliphatically unsaturated functional group. Examples of suitable compounds containing an unsaturated group include, but are not limited to, unsaturated polyethers such as alkyl-capped allyl polyethers, vinyl functionalized alkyl capped allyl or methylallyl polyethers; terminally unsaturated amines; alkynes; C2-C45 olefins, in one embodiment alpha olefins; unsaturated
epoxides such as allyl glycidyl ether and vinyl cyclohexene-oxide; terminally unsaturated acrylates or methyl acrylates; unsaturated aryl ethers; unsaturated aromatic hydrocarbons; unsaturated cycloalkanes such as trivinyl cyclohexane; vinyl-functionalized polymer or oligomer; and vinyl- functionalized and/or terminally-unsaturated alkenyl-silanes and/or silicones; unsaturated fatty acids; unsaturated fatty esters; or combinations of two or more thereof. Illustrative examples of such unsaturated substrates include, but are not limited to, ethylene, propylene, isobutylene, 1-hexene, 1-octene, 1-octadecene, styrene, alpha-methylstyrene, cyclopentene, norbornene, 1,5-hexadiene, norbomadiene, vinylcyclohexene, allyl alcohol, allyl-terminated polyethyleneglycol, allylacrylate, allyl methacrylate, allyl glycidyl ether, allyl-terminated isocyanate-or acrylate prepolymers, polybutadiene, allylamine, methallyl amine, acetylene, phenylacetylene, vinyl- pendent or vinyl-terminal polysiloxanes, vinylcyclosiloxanes, vinylsiloxane resins, vinyl-functional synthetic or natural minerals, etc.
[0064] Unsaturated polyethers suitable for the hydrosilylation reaction include
polyoxyalkylenes having the general formula:
R26(OCH2CH2)z(OCH2CHR28)w— OR27; and/or
R270(CHR28CH20)w(CH2CH20)z— CR292— C≡C— CR29 2(OCH2CH2)z(OCH2CHR28)wR27 wherein R26 denotes an unsaturated organic group containing from 2 to 10 carbon atoms such as allyl, methylallyl, propargyl or 3-pentynyl. When the unsaturation is olefmic, it is desirably terminal to facilitate smooth hydrosilylation. However, when the unsaturation is a triple bond, it may be internal. R 27 is independently hydrogen, vinyl, allyl, methallyl, or a polyether capping group of from 1 to 8 carbon atoms such as the alkyl groups: CH3, n-C4H , t-C4t¾ or i-CsHn, the acyl groups such as CH3COO, t-C4H COO, the beta-ketoester group such as CH3C(0)CH2C(0)0, or a
28 29
trialkylsilyl group. R and R are monovalent hydrocarbon groups such as the C1-C20 alkyl groups, for example, methyl, ethyl, isopropyl, 2-ethylhexyl, dodecyl and stearyl, or the aryl groups, for example, phenyl and naphthyl, or the alkaryl groups, for example, benzyl, phenylethyl and nonylphenyl, or the cycloalkyl groups, for example, cyclohexyl and cyclooctyl. R29 may also be
28 29
hydrogen. Methyl is particularly suitable for the R and R groups. Each occurrence of z is 0 to 100 inclusive and each occurrence of w is 0 to 100 inclusive. In one embodiment, the values of z and w are 1 to 50 inclusive.
[0065] As indicated above, in one embodiment the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in
order to produce the silylated product, wherein the catalyst is a complex of the Formula (I) or an adduct thereof. As indicated above, in one embodiment the present invention provides a process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof. In one embodiment, the silylated product from the process comprises a
hydrosilylated product. In one embodiment, the silylated product from the process comprises a dehydrogenative silylated product. In one embodiment, the product comprises a mixture of hydrosilylated and dehydrogenative silylated product.
[0066] The manner or order in which the respective components for carrying out the process are added to one another is not particularly limited and can be chosen as desired. In one
embodiment, the silylhydride can be added to a mixture containing the metal complex and the unsaturated olefin. In another embodiment, the unsaturated olefin can be added to a mixture containing the metal complex and the silylhydride. In still another embodiment, a mixture of silylhydride and unsaturated olefin can be added to a mixture of metal complex, silylhydride and unsaturated olefin. It will be appreciated that the first mixtures in the above embodiments may be heated or preliminarily reacted prior to addition of the remaining components
[0067] Effective catalyst usage for silylation ranges from 0.001 mole percent to 10 mole percent based on the molar quantity of the alkene to be reacted. Preferred levels are from 0.005 to 1 mole percent. Reaction may be run at temperatures from about -10°C up to 300°C, depending on the thermal stability of the alkene, silyl hydride and the specific pyridine di-imine complex.
Temperatures in the range, 10 - 100°C, have been found to be effective for most reactions. Heating of reaction mixtures can be done using conventional methods as well as with microwave devices.
[0068] The catalyst composition can be provided for either the dehydrogenative silylation or hydrosilylation reactions in an amount sufficient to provide a desired metal concentration. In one embodiment, the concentration of the catalyst is about 5% (50000 ppm) or less based on the total weight of the reaction mixture; about 1% (10000 ppm) or less; 5000 ppm or less based on the total weight of the reaction mixture; about 1000 ppm or less; about 500 ppm or less based on the total weight of the reaction mixture; about 100 ppm or less; about 50 ppm or less based on the total weight of the reaction mixture; even about 10 ppm or less based on the total weight of the reaction mixture. In one embodiment, the concentration of the catalyst is from about 10 ppm to about 50000 ppm; about 100 ppm to about 10000 ppm; about 250 ppm to about 5000 ppm; even about 500 ppm
to about 2500 ppm. In one embodiment, the concentration of the metal atom is from about 100 to about 1000 ppm based on the total weight of the reaction mixture. The concentration of the metal (e.g., cobalt) can be from about 1 ppm to about 5000 ppm; from about 5 ppm to about 2500 ppm; from about 10 ppm to about 1000 ppm, even from about 25 ppm to about 500 ppm. Here as elsewhere in the specification and claims, numerical values can be combined to form new and non- disclosed ranges.
[0069] The silylation reactions of this invention can be run at subatmospheric and supra- atmospheric pressures. Typically, pressures from about 1 atmosphere (0.1 MPa) to about 200 atmospheres (20 MPa), preferably to about 50 atmospheres (5.0 MPa), are suitable. Higher pressures are effective with volatile and/or less reactive alkenes which require confinement to enable high conversions.
[0070] In one embodiment, the catalysts are useful for dehydrogenative silylation of a composition containing a silyl hydride and a compound having at least one unsaturated group. The process includes contacting the composition with a suitable metal complex, either supported or unsupported, to cause the silyl hydride to react with the compound having at least one unsaturated group to produce a dehydrogenative silylation product, which may contain the metal complex catalyst. The dehydrogenative silylation reaction can be conducted optionally in the presence of a solvent. If desired, when the dehydrogenative silylation reaction is completed, the metal complex can be removed from the reaction product by magnetic separation and/or filtration. These reactions may be performed neat, or diluted in an appropriate solvent. Typical solvents include benzene, toluene, diethyl ether, etc. It is preferred that the reaction is performed under an inert atmosphere.
[0071] Because the double bond of an alkene is preserved during the dehydrogenative silylation reaction employing these cobalt catalysts, a singly-unsaturated olefin may be used to crosslink silyl-hydride containing polymers. For example, a silyl-hydride polysiloxane, such as Momentive SL6020 Dl (MDisDH 3oM), may be reacted with 1-octene in the presence of the cobalt catalysts of this invention to produce a crosslinked, elastomeric material. A variety of new materials can be produced by this method by varying the hydride polymer and length of the olefin used for the crosslinking. Accordingly, the catalysts used in the process of the invention have utility in the preparation of useful silicone products, including, but not limited to, coatings, for example release coatings, room temperature vulcanizates, sealants, adhesives, products for agricultural and personal care applications, and silicone surfactants for stabilizing polyurethane foams.
[0072] The cobalt complexes disclosed herein can be used as a catalyst for various reactions including, for example, the hydrosilylation of a composition containing a silyl hydride and a compound having at least one aliphatically unsaturated group. The hydrosilylation process includes contacting the composition with a cobalt complex of the Formula (I), either supported or unsupported, to cause the silyl hydride to react with the compound having at least one aliphatically unsaturated group to produce a hydrosilylation product. The hydrosilylation product may contain the components from the catalyst composition. The hydrosilylation reaction can be conducted optionally in the presence of a solvent, at subatmospheric or supra-atmospheric pressures and in batch or continuous processes. The hydrosilylation reaction can be conducted at temperatures of from about -10 °C to about 200 °C. If desired, when the hydrosilylation reaction is completed, the catalyst composition can be removed from the reaction product by filtration.
[0073] It will be appreciated that the reaction of a silyl hydride with an unsaturated compound can provide a mixture of hydrosilylated and dehydrogenatively silylated products. In one embodiment, a majority of the products is the hydrosilylated product.
[0074] The cobalt complexes of the invention are, in embodiments, efficient and selective in catalyzing hydrosilylation reactions. For example, when the metal complexes of the invention are employed in the hydrosilylation of a silyl hydride and a compound containing an unsaturated group, the reaction products are essentially free of unreacted unsaturated compound and/or any
dehydrogenative silylated products. In one embodiment, the reaction products do not contain the unreacted and its isomerization products. As used herein, "essentially free" is meant no more than 10 wt. %, no more than 5 wt. %, no more than 3 wt. %; even no more than 1 wt. % based on the total weight of the hydrosilylation product. "Essentially free of internal addition products" is meant that silicon is added to the terminal carbon.
[0075] Hydrosilylation and dehydrogenative silylation reactions are conducted on large scales to produce various organic and inorganic materials, including additives to household items and release coatings. The disclosed approach can see immediate commercial application for these processes, which offers a cheaper yet competitive alternative to the current precious-metal-based practices. More importantly, the present reactions provide higher selectivity and fewer by-products for certain substrates compared to existing processes.
[0076] The following examples are intended to illustrate, but in no way limit the scope of the present invention. All parts and percentages are by weight and all temperatures are in degrees Celsius unless explicitly stated otherwise. All the publications and the U.S. patents referred to in the application are hereby incorporated by reference in their entireties.
EXAMPLES
General considerations
[0077] All air- and moisture-sensitive manipulations were carried out using standard Schlenk techniques or in an MBraun inert atmosphere dry box containing an atmosphere of purified nitrogen. Solvents for air- and moisture-sensitive manipulations were dried and deoxygenated by passing through solvent system columns and stored with 4 A molecular sieves in the dry box.
Benzene -de was purchased from Cambridge Isotope Laboratories, dried over sodium and stored with 4 A molecular sieves in the dry box. The 2,2';6'2"-terpyridine (terpy) ligand was obtained from Strem, dried under high vacuum overnight and brought into the dry box. Liquid substrates were dried over LiAlH4 or CaH2 and degased under high vacuum before use.
[0078] NMR spectra were acquired on a Varian INOVA-500 or Bruker-500 MHz spectrometer. The chemical shifts (δ) of 1H NMR spectra are given in parts per million and referenced to the solvent residual of benzene -de (7.16 ppm).
[0079] In the equations depicting the hydrosilylation and dehydrogenative silylation reactions in Examples 13 - 16, the abbreviation "[Si]" is used in the formulae of the products to show the attachment of the reactive silicon atom to the unsaturated substrate. The remaining groups on the silicon atom are omitted for clarity. However, the specific reaction products formed are identified in the examples.
Example 1 : Synthesis of alloxydiphenylsilane
+ Et3NHCI
[0080] The synthesis of alloxydiphenylsilane follows a modified literature procedure as described by Bergens, S. H.; Noheda, P.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1992, 1 14, 2121-2128 and was carried out in air. A solution of allyl alcohol (2.9 g, 50 mmol) and triethylamine (5.1 g, 50 mmol) in Et20 (250 mL) was cooled in an ice bath. With rapid stirring,
chlorodiphenylsilane (1 1 g, 50 mmol) was added dropwise to the solution. Large quantities of a fluffy white precipitate (Et3NHCl) were observed immediately. The mixture was warmed to room temperature and stirred for 1 h. The resulting solution was filtered through Celite and washed with Et20. The filtrate was concentrated and yielded a colorless oil, which upon distillation (84 - 85 °C, 65 mmTorr) afforded the desired product as a colorless oil in 80% yield. 1H NMR (400 MHz, benzene-*/ ) δ 7.74 - 7.62 (m, 4H), 7.27 - 7.06 (m, 6H), 5.81 (ddt, J = 17.1 , 10.6, 4.6 Hz, 1H), 5.69
(s, 1H), 5.31 (dq, J= 17.1, 1.8 Hz, 1H), 5.00 (dq, J= 10.6, 1.8 Hz, 1H), 4.16 (dt, J= 4.6, 1.8 Hz, 2H). 13C NMR (126 MHz, C6D6) δ 136.73, 135.11, 134.31, 130.66, 128.39, 128.25, 128.06, 127.87, 114.77, 65.60.
Example 2: Synthesis of alloxydimethylsilane
^^OH + Me2SiHCI ΕΪ3Ν' Et2°>, ^^OSMe2H + Et3NHCI
r.t., 1 h
[0081] Alloxydimethylsilane was prepared in a manner similar to alloxydiphenylsilane. A solution of allyl alcohol (2.9 g, 50 mmol) and triethylamine (5.1 g, 50 mmol) in Et20 (250 mL) was cooled in an ice bath. While rapid stirring, the solution was added with chlorodimethylsilane (4.7 g, 50 mmol) dropwise. Large quantities of a fluffy white precipitate (Et3NHCl) were observed immediately. The mixture was warmed to room temperature and stirred for 1 hour. The resulting solution was filtered through Celite and washed with Et20. The filtrate was concentrated to yield a colorless oil, which following factional distillation (79 - 83 °C), afforded the product as a colorless oil in 50% yield.1H NMR (400 MHz, chloroform-^ ) δ 5.93 (ddt, J= 17.2, 10.1, 5.0 Hz, 1H), 5.26 (dq, J= 17.2, 1.8 Hz, 1H), 5.12 (dq, J= 10.4, 1.6 Hz, 1H), 4.68 - 4.55 (m, 1H), 4.18 (dt, J= 5.0, 1.7 Hz, 2H), 0.23 (s, 3H), 0.23 (s, 3H).
Example 3: Synthesis of (terpy Co(CH TMS
[0082] The solution of py2Co(CH2TMS)2 (390 mg, 1 mmol) in pentane (20 mL) was prepared following literature procedures and cooled to -35 °C. Zhu, D.; Janssen, F. F. B. J.;
Budzelaar, P. H. M. Organometallics 2010, 29, 1897. The terpyridine ligand (233 mg, 1 equiv) was dissolved in pentane and added into the solution containing the cobalt compound. An immediate color change from green into purple was observed. The solution was stirred at room temperature for 0.5 hours, followed by removal of the volatile components in vacuo. The residue was dissolved in pentane and filtered through Celite to yield (terpy)Co(CH2TMS)2. The solution of
(terpy)Co(CH2TMS)2 in Et20 was stirred for 4 hours to generate the mono-neosilyl complex and following recrystallization from toluene/pentane at -35 °C yielded a purple solid. 1H NMR (400 MHz, benzene-^) δ 12.23 (d, J = 6.2 Hz, 3H), 8.64 (t, J = 7.6 Hz, 2H), 8.01 (t, J = 6.8 Hz, 2H), 7.55 (d, J = 8.2 Hz, 2H), 7.02 (d, J = 7.5 Hz, 3H), 1.15 (s, 2H), -0.13 (d, J = 5.0 Hz, 9H).
[0083] In a glove box, to a purple solution of (terpy)Co(CH2TMS) (38 mg, 0.1 mmol) in toluene was treated with alloxydiphenylsilane (24 mg, 0.1 mmol) and stirred for 4 hours. A purple solution was observed following the addition. The solution was filtered through Celite and concentrated under vacuum. The resulting solution was layered with pentane and stored at -35 °C for 2 days and yielded purple crystals identified as the desired product. 1H NMR (300 MHz, benzene-d6) δ 7.85 (dd, J = 7.7, 1.0 Hz, 1H), 7.75 - 7.57 (m, 3H), 7.34-6.74 (m, 11H), 6.67-6.60 (m, 3H), 6.54 - 6.43 (m, 2H), 6.36 (td, J = 6.7, 1.5 Hz, 1H), 6.25 (td, J = 6.5, 1.2 Hz, 1H), 5.47 (dd, J= 10.2, 6.8 Hz, 1H) (s, 1H), 4.43 (t, J = 9.2 Hz, 1H), 3.95-4.12 (m, 1H) 3.24 - 3.12 (m, 1H), 2.77 (d, J = 12.5 Hz, 1H). 13C NMR (126 MHz, C6D6) δ 149.65, 148.17, 147.88, 145.19, 144.92, 144.51, 143.10, 139.71, 132.46, 132.11, 129.33, 128.0, 127.8, 127.6, 127.14, 126.68, 125.94, 125.54, 119.82, 119.62, 119.40, 119.01, 118.99, 117.81, 115.69, 74.94, 68.85, 56.32.
Example 5: Synthesis of (terpy Co(Me SiOC^HQ
[0084] This compound was prepared in a manner similar to (terpy)Co(Ph2SiOC3H5). In a glove box, to a purple solution of (terpy)Co(CH2TMS) (38 mg, 0.1 mmol) in pentane (1 mL) was treated with alloxydimethylsilane (16 mg, 0.12 mmol) and stirred for 6 hours. A purple solution and precipitate formation were observed. The solid was isolated through filtration and purified by dissolving in toluene and passing through Celite. The resulting solution was layered with pentane and stored at -35 °C for 1 day and yielded purple crystals identified as the desired product. 1H NMR
(300 MHz, benzene-^) δ 7.97 (dd, J= 8.0, 0.9 Hz, 1H), 7.86 (dd, J= 7.8, 0.9 Hz, 1H) 7.75 (d, J = 8.2 Hz, 1H), 7.68 (d, J= 6.6 Hz, 1H), 7.64 (d, J= 8.3, 1H), 7.25 (t, J= 7.6 Hz, 2H), 7.02 (d, J= 6.4 Hz, 1H), 6.93 - 6.75 (m, 2H), 5.27 (dd, J= 10.5, 6.2 Hz, 1H), 4.25 (t, J= 10.4 Hz, 1H), 3.89-3.72 (m, 1H), 3.39 (dd, J= 9.2, 2.0 Hz, 1H), 2.96 (dd, J= 12.4, 1.9 Hz, 1H), -0.37 (s, 3H), -1.11 (s, 3H).
General Procedure for Catalyst screening of the silylation of 1-octene with triethoxysilane
[0085] In a glove box, 1-octene (112 mg, 1 mmol) and triethoxysilane (164 mg, 1 mmol) were charged into a vial equipped with a stir bar. The solid cobalt precursor (2-3 mg, 0.5 mol%)
was charged into a separate vial and then added to the vial containing substrates. The vial was sealed with a cap and stirred. After 1 hour, the reaction was quenched by exposure to air. The product mixture was analyzed by GC prior to filtration. Subsequently, it was filtered through a plug of silica gel (Fluka®, high-purity grade, pore size 60 A, 40-63 um particle size) typically used for flash chromatography. The resulting eluate was stripped under vacuum and analyzed by 1 H and 13 C NMR spectroscopy. The yields are based on conversion of 1-octene.
C
The reaction products are identified in the equation above. n-Octyltriethoxysilane, (Product A), is the anti-Markovnikov hydrosilylation product. 2-Triethoxysilyloctane, (Product B), is the
Markovnikov hydrosilylation product. Product C is the allylic silane (2-Octenyltriethoxysilane) produced via dehydrogenative silylation. Octane was formed in equimolar amounts with Product C.
Example 6: Hydrosilylation of 1-octene with triethoxysilane using (terpy^ofPh^SiOC^HQ in the glove box
[0086] In a glove box, 1-octene (112 mg, 1 mmol) and triethoxysilane (164 mg, 1 mmol) were weighed into a vial equipped with a stir bar. Purple (terpy)Co(Ph2SiOC3H5) (2 mg, 0.5 mol%) was weighed into a separate vial, and was subsequently combined with the substrates. The vial was stirred at ambient temperature for 1 hour. The reaction was quenched by exposure to air. The product mixture was processed as detailed in the general procedure above. GC and 1H NMR spectroscopy showed >95% yield of anti-Markovnikov hydrosilylation product and about 2% of the dehydrogenative silylation product.
Example 7: Hydrosilylation of 1-octene with triethoxysilane using (terpy Co(Me7SiOC3HQ in the glove box
[0087] In a glove box, 1-octene (112 mg, 1 mmol) and triethoxysilane (164 mg, 1 mmol) were weighed into a vial equipped with a stir bar. Purple (terpy)Co(Me2SiOC3H5) (2 mg, 0.5 mol%) was weighed into a separate vial, and was subsequently combined with the substrates. The contents of the vial were stirred at room temperature for 1 hour. The reaction was quenched by exposure to air. The reaction was quenched by exposure to air. The product mixture was processed as detailed in the general procedure above. GC and 1H NMR spectroscopy showed 90% yield of anti- Markovnikov hydrosilylation product and 9% dehydrogenative silylation product.
Example 8: Bench-top hydrosilylation of 1-octene with triethoxysilane using
(terpy)Co(Pri7SiOC HO under Ar
[0088] A 50 mL Schlenk flask equipped with a stir bar was charged with 1-octene (112 mg, 1 mmol) and triethoxysilane (164 mg, 1 mmol) in the glove box. The flask was sealed with a glass stopper and transferred out of the box. (terpy)Co(Ph2SiOC3H5) (2 mg, 0.5 mol%) was charged into a vial, brought out of the box and exposed to air for 10 minutes. The solid catalyst was added into the Schlenk flask under an Ar counterflow. The flask was sealed with a glass stopper and stirred for 1 hour. The reaction was quenched by exposure to air. The reaction mixture was analyzed by GC and 1H NMR spectroscopy, which established >98% yield of anti-Markovnikov hydrosilylation product and trace dehydrogenative silylation product.
Examples 9 and 10: Siloxane cross-linking using (terpy^ofPh^SiOC^HQ and
(terpy)Co(Me SiOC3_H in the glove box under N?
SL6100
cross-linked silicone
SL6100
cross-linked silicone
toluene (1 drop)
r.t., 1 h
[0089] All operations were done in a nitrogen filled glove box. For each example,
Momentive SL6100 (1 g) and Momentive SL6020 Dl (44 mg) were weighed into a vial equipped with a stir bar. The purple solid, (terpy)Co(Pfi2SiOC3H5) (5 mg, 1 mol%) (Example 9) or
(terpy)Co(Me2SiOC3H5) (4 mg, 1 mol%) (Example 10), was weighed into a separate vial, and was subsequently combined with the substrates. During 1 h, formation of gel was observed in both vials.
Example 11 - Preparation of (4-NMe -Ph-Terpy)CoCH TMS
[0090] In a nitrogen filled glove box, a scintillation vial was charged with a suspension of 0.154 g (0.319 mmol) (4-NMe2-Ph-Terpy)CoCl2 in approximately 10 mL of diethyl ether. The mixture was chilled at -35 °C for 10 minutes. With vigorous stirring, a diethyl ether solution of (trimethylsilyl)methyllithium (0.060 g, 0.639 mmol in 2 mL diethyl ether) was added dropwise to the chilled suspension.
[0091] During the addition, a color change to dark purple was observed. The mixture was stirred at 23 °C for 12 hours, after which it was filtered through Celite and dried in vacuo. The mixture was extracted with approximately 10 mL benzene, filtered and subsequently dried in vacuo to yield a fine dark purple solid identified as (4-NMe2- Ph-Terpy)CoCH2TMS. 1H NMR (benzene- d6, 23 °C): δ = 12.29 (d, 6 Hz, 2H), 8.68 (t, 8 Hz, 2H), 8.02 (t, 7 Hz, 2H), 7.93 (d, 8 Hz, 2H), 7.52 (m, 4H), 6.59 (d, 9 Hz, 2H), 2.45 (s, 6H), -0.08 (s, 9H), one signal missing (not detected).
Example 12 - Silylation of 1-octene with MD M using (4-NMe?-Ph-terpy)CoNs
neat, 23 °C, 1 h
[0092] In a nitrogen-filled drybox, a scintillation vial was charged with 0.100 g (0.891 mmol) of 1-octene and approximately 0.005 g (0.009 mmol) (4-NMe2-Ph-terpy)CoNs (1 mol %). MDHM (0.198 g, 0.891 mmol) was then added to the mixture and the reaction was stirred at room temperature for 1 hour, after which the mixture was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The crude product mixture was analyzed by GC. Volatiles were then removed from the crude mixture product and the resulting
1 13
mixture was analyzed by H and C NMR spectroscopy.
[0093] The results showed 29% anti-Markovnikov hydrosilylation product (A), 36% total dehydrogenative silylation products (B and C) and 35% octane (D). Note that two dehydrogenative silylation products were produced, one with vinyl unsaturated (B) and the other with allyl unsaturation (C).
Example 13 - Procedure for dehydrogenative hydrosilylation of 1-octene with EfrSiH
1 ,554 fCo¾, it. 1
[0094] In a nitrogen filled glove box, a scintillation vial was charged with a stir bar, 0.112 g (1 mmol) of 1-octene and 0.116 g (1 mmol) of triethylsilane. (Terpy)CoCH2TMS (0.002 g, 0.5 mol%) was then added into the reaction mixture as a solid. The vial was sealed with a cap and stirred at 23 °C for 1 hour, after which the reaction was quenched by exposure to air. The product mixture was filtered through silica gel and eluted with hexane. The resulting solution was dried
1 13
under vacuum and analyzed by GC, H and C NMR spectroscopy. The yields are based on
conversion of 1-octene. The yield of the hydrosilylation product (A), octyltriethylsilane, was 18% and that of the allylic dehydrogenative silylation product (B), 2-octenyltriethylsilane, was 41%. Note that an equimolar amount of the hydrogenated product (C), octane, was also formed.
Example 14: Silylation of 1 -octene with l-(2-trimethylsilylethyl)-l,l,3,3,-tetramethyldisiloxane
[0095] In a nitrogen-filled drybox, a scintillation vial was charged with 0.050 g (0.446 mmol) of 1-octene and approximately 0.001 g (0.004 mmol) (Terpy)CoCH2TMS (1 mol %). l-(2- trimethylsilylethyl)-l,l,3,3,-tetramethyldisiloxane (CAS Number 154455-22-8) (0.117 g, 0.446 mmol) was then added to the mixture and the reaction was stirred at room temperature for 1 hour, after which the mixture was quenched by exposure to air. The crude product mixture was analyzed by GC. It was then filtered through silica gel and eluted with hexane. Volatiles were then removed
1 13
and the resulting concentrate was analyzed by H and C NMR spectroscopy.
neat, 23 °C, 1 h
[0096] The hydrosilylation product (A), (CHs^S^t^S^CHs^OS^CHs^CgHn, was obtained in 18% yield, while the dehydrogenative silylation product (B),
(CH3)3SiC2H4Si(CH3)20Si(CH3)2CgHi5 , and the hydrogenated product (C), octane, were formed in equimolar amounts, 41%.
Example 15: Silylation of 1-octene with (2-Trimethylsilyl)ethyldimethylsilane,
(CH3 SiC9H4Si(CH3 9H, using TerpyCoCH9TMS
[0097] In a nitrogen-filled drybox, a scintillation vial was charged with 0.050 g (0.446 mmol) of 1-octene and approximately 0.001 g (0.004 mmol) TerpyCoCE^TMS (1 mol %). (2- Trimethylsilyl)ethyldimethylsilane (CAS Number 6231-75-0), (0.072 g, 0.446 mmol) was then added to the mixture and the reaction was stirred at room temperature for 1 hour, after which the mixture was quenched by exposure to air. The product mixture was filtered through silica gel and
eluted with hexane. The crude product mixture was analyzed by GC. Volatiles were then removed
1 13
from the crude product mixture and the residue was analyzed by H and C NMR spectroscopy.
neat, 23 °C, 1 h
[0098] The anti-Markovnikov product, l-(octyldimethylsilyl),2-(trimethylsilyl)ethane, (A), was obtained in 60% yield, and the allylic dehydrogenative silylation product (B), l-(2- octenyldimethylsilyl),2-(trimethylsilyl)ethane in 20% yield, along with an equimolar quantity of octane.
Examples 16 - 20: Silylation of Vinylcyclohexene oxide (3-vinyl-7-oxabicvclor4.1.01heptane) with MDHM with various TerpyCoNs Catalysts
[0099] These examples illustrate the use of various TerpyCoNs catalysts for the
simultaneous hydrosilylation and dehydrogenative silylation of vinylcyclohexene oxide (VCHO). The catalysts differ in the substitution at the 4-position of the terpyridine ligand. Thus, in Example 16, the unsubstituted ligand was used, in Example 17, the 4-fluorophenyl, in Example 18, the 4- dimethylaminophenyl, in Example 19, the 4-mesityl and in Example 20, the 4-(pyrrolidin-l-yl).
[00100] All reactions were conducted in a nitrogen-filled drybox. In each case, a scintillation vial was charged with 0.112 g (0.899 mmol) of 3-vinyl-7-oxabicyclo[4.1.0]heptane (mixture of isomers) and (0.005 mmol, 1 mol %>) of the desired modified terpyCoNs catalysts (see Table 1 below for structures). MDHM (0.100 g, 0.449 mmol) was then added to the mixture and the reaction was stirred at 23 °C for 2 minutes. The product mixture was quenched by exposure to air. It was filtered through a plug of silica gel (Fluka®, high-purity grade, pore size 60 A, 40-63 μιη particle size, typically used for flash chromatography) and eluted with hexane. The resulting
1 13
solution was stripped under vacuum and was analyzed by GC, H and C NMR spectroscopy. The yields are based on conversion of 3-vinyl-7-oxabicyclo[4.1.0]heptane.
[00101] The four products shown in the equation above were identified in the reaction mixture. Product (a) is the result of dehydrogenative silylation, while (b) is the hydrosilylation product. The reduced and isomerized by-products of VCHO are (c) and (d), respectively. Table 1 shows that equimolar amounts of the dehydrogenatively silylated product (a) and hydrogenated VCHO (b) were obtained. In general, dehydrogenative silylation product (a) exceeded the hydrosilylation product (b).
TABLE 1 : VCHO Conversion and Product Formation in Examples 16 - 20.
[00102] While, due to air and moisture intolerance of the cobalt catalysts, these catalyzed processes should be performed under air and moisture free conditions, it has now been illustrated that employment of a silyl-olefin protecting group to stabilize the cobalt catalysts yields air- stable cobalt catalysts for hydrosilylation and dehydrogenative silylation.
[00103] While the above description contains many specifics, these specifics should not be construed as limitations on the scope of the invention, but merely as exemplifications of preferred embodiments thereof. Those skilled in the art will envision many other possible variations that are within the scope and spirit of the invention as defined by the claims appended hereto.
Claims
What is claimed is:
1. A complex of the Formula:
wherein each occurrence of R1- R11 is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R^R11, other than hydrogen, optionally contain at least one heteroatom; optionally any two of R!-Rn vicinal to one another, R4- R5, and/or R7-R8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, an aralkyl group, or an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
2. The complex of claim 1, wherein R!-Rn are hydrogen.
22 23 22 23
3. The complex of claim 1, wherein L is -C(R )2-Si(R )3 where R and R are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted
C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
4. The complex of claim 4, wherein R!-Rn are hydrogen.
5. The complex of claim 1, wherein the catalyst is of the formula:
CH2Si(C H3)3
6. The complex of claim 1, wherein at least one of R -R is chosen from an aryl group or a substituted aryl group.
7. The complex of claim 6, wherein the substituted aryl group is chosen from tolyl, xylyl, naphthyl, mesityl, aniline, fluorophenyl, or a combination of two or more thereof.
8. The complex of claim 1, wherein R!-R5 and R7-Rn are hydrogen, and R6 is chosen from pyrrolidino, flourophenyl, aniline, or mesityl.
9. The complex of claim 1, wherein the complex is of the formula:
CH2Si(CH3)3
10. A process for producing a silylated product comprising reacting a mixture comprising (a) an unsaturated compound containing at least one unsaturated functional group, (b) a silyl hydride containing at least one silylhydride functional group, and (c) a catalyst, optionally in the presence of a solvent, in order to produce the silylated product, wherein the catalyst is a complex of the Formula (IV) or an adduct thereof:
1 18
wherein each occurrence of R - R is independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C5-C18 cycloalkyl, a C5-C18 substituted cycloalkyl, a C6-C18 aryl, a substituted C6-C18 aryl, or an inert substituent wherein one or more of R^R11, other than hydrogen, optionally contain at least one heteroatom; optionally any two of R!-Rn vicinal to one another, R4- R5, and/or R7-R8 taken together may form a ring being a substituted or unsubstituted, saturated, or unsaturated cyclic structure; and L is chosen from hydrogen, a CI -CI 8 alkyl, CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted C6-C18 aryl group, an alkaryl group, or an aralkyl group, an alkyl trialkylsilyl, where L optionally contains at least one heteroatom.
11. The process of claim 10, wherein R!-Rn are hydrogen.
22 23 22 23
12. The process of claim 10, wherein L is -C(R )2-Si(R )3 where R and R are independently hydrogen, a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C18 aryl, a substituted
C6-C18 aryl, or an inert substituent, and R 22 and R 23 optionally contain at least one heteroatom.
13. The process of claim 12, wherein R!-Rn are hydrogen.
14. The process of claim 10 wherein the catalyst is of the formula:
15. The process of claim 10, wherein at least one of R -R is chosen from an aryl group or a substituted aryl group.
The process of claim 15, wherein the substituted aryl group is aniline.
The process of claim 10, wherein the complex is of the formula:
CH2Si(CH3)3
18. The process of any of claims 10-17, further comprising removing the complex and/or derivatives thereof from the silylated product.
19. The process of any of claims 10-18, wherein the silylated product comprises a hydrosilylation product.
20. The process of any of claims 10-18, wherein the silylated product comprises a dehydrogenatively silylated product.
21. The process of any of claims 10-18, wherein the silylated product comprises a mixture of (i) a hydrosilylation product, and (ii) a dehydrogenative silylated product.
22. The process of any of claims 10-21, wherein the unsaturated compound (a) is chosen from a linear or branched olefin; a cycloalkene; an alkyl-capped allyl polyether; a vinyl-functional alkyl-capped allyl or methallyl polyether; an alkyl-capped terminally unsaturated amine; an alkyne; a terminally unsaturated acrylate or methacrylate; an unsaturated aryl ether; a vinyl-functionalized
polymer or oligomer; a vinyl-functionalized and/or terminally-unsaturated alkenyl-functional silane; and/or silicone; an unsaturated fatty acid; an unsaturated ester; or combinations of two or more thereof.
23. The process of any of claims 10-22, wherein the reaction is conducted under an inert atmosphere.
24. The process of any of claims 10-23, wherein the reaction is carried out at a temperature of -10°C to 300°C.
25. The process according to any of claims 10-24, wherein the silyl hydride comprises a hydride fluid chosen from one or a combination of compounds of the formulas:
MaMH bDcDH dTeTH fQg;
R30 3Si(CHR30)xSiOSi R30 2(OSi R30 2)yOSi R30 2H,
R30 3Si(CHR30)xSi R30 2H
24
where each R is independently a substituted or unsubstituted aliphatic or aromatic hydrocarbyl group; X is halogen, alkoxy, acyloxy, or silazane; m is 0-3; p is 1-3, with the proviso that the
25
tetrvalency of silicon is preserved; M represents a monofunctional group of formula R 3SiOi/2; a D
25
represents a difunctional group of formula R 2Si02/2; a T represents a trifunctional group of formula R25Si03/2; Q represents a tetrafunctional group of formula Si04/2; MH represents
25 H H 25 25
HR 2SiOi/2, T represents HSi03/2, and D group represents R HSi02/2; each occurrence of R is independently a Ci-Cig alkyl, a Ci-Cig substituted alkyl, a C6-C14 aryl or substituted aryl, wherein
25
R optionally contains at least one heteroatom; subscripts a, b, c, d, e, f, and g are such that the
30 molar mass of the compound is between 100 and 100,000 Dalton; each occurrence of R is independently a CI -CI 8 alkyl, a CI -CI 8 substituted alkyl, a C6-C14 aryl or substituted aryl; x is 1- 8, and y is 0-10.
26. The process of any of claims 10-26, wherein the complex is immobilized on a support.
27. The complex of claim 26, wherein the support is chosen from carbon, silica, alumina, MgCl2, zirconia, polyethylene, polypropylene, polystyrene, poly(aminostyrene), sulfonated polystyrene, or a combination of two or more thereof.
28. A composition produced by the process of any of claims 10-27, wherein the composition contains the catalyst or derivatives thereof.
29. The composition of claim 28 comprising at least one component selected from the group of silanes, silicone fluids, and crosslinked silicones, or a combination of two or more thereof.
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|---|---|---|---|
| EP14815501.3A EP3071586A1 (en) | 2013-11-19 | 2014-11-19 | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation |
| CN201480073588.1A CN105916870A (en) | 2013-11-19 | 2014-11-19 | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation |
| JP2016532096A JP2016540753A (en) | 2013-11-19 | 2014-11-19 | Cobalt catalysts and their use for hydrosilylation and dehydrogenation silylation |
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| US201462031463P | 2014-07-31 | 2014-07-31 | |
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| PCT/US2014/066356 WO2015077306A1 (en) | 2013-11-19 | 2014-11-19 | Cobalt catalysts and their use for hydrosilylation and dehydrogenative silylation |
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| US (2) | US9381506B2 (en) |
| EP (2) | EP3071552A1 (en) |
| JP (1) | JP2016540753A (en) |
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Cited By (3)
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| JP2018522946A (en) * | 2015-07-24 | 2018-08-16 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Dehydrogenated silylation, hydrosilylation and crosslinking using pyridinediimine cobalt carboxylate catalyst |
| CN113201018A (en) * | 2021-04-30 | 2021-08-03 | 安徽大学 | Mn (II) complex with AIE property and living cell mitochondria targeting function and preparation method and application thereof |
| US11760839B2 (en) | 2019-11-26 | 2023-09-19 | Dow Silicones Corporation | Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955555A (en) | 1996-12-17 | 1999-09-21 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene |
| US6461994B1 (en) | 1998-09-12 | 2002-10-08 | Bp Chemicals Limited | Polymerization catalyst |
| US6657026B1 (en) | 1998-03-12 | 2003-12-02 | Bp Chemicals Limited | Polymerization catalysts |
| US7053020B2 (en) | 2002-09-25 | 2006-05-30 | Shell Oil Company | Catalyst systems for ethylene oligomerisation to linear alpha olefins |
| US7259220B1 (en) | 2006-07-13 | 2007-08-21 | General Electric Company | Selective hydrosilylation method |
| US7442819B2 (en) | 2004-07-09 | 2008-10-28 | E. I. Du Pont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
| US7507775B2 (en) | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
| US20110009565A1 (en) * | 2009-07-10 | 2011-01-13 | Delis Johannes G P | Hydrosilylation Catalysts |
| US8236915B2 (en) | 2009-07-10 | 2012-08-07 | Momentive Performance Materials Inc. | Hydrosilylation catalysts |
Family Cites Families (64)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3296291A (en) | 1962-07-02 | 1967-01-03 | Gen Electric | Reaction of silanes with unsaturated olefinic compounds |
| US3159601A (en) | 1962-07-02 | 1964-12-01 | Gen Electric | Platinum-olefin complex catalyzed addition of hydrogen- and alkenyl-substituted siloxanes |
| US3220972A (en) | 1962-07-02 | 1965-11-30 | Gen Electric | Organosilicon process using a chloroplatinic acid reaction product as the catalyst |
| US3775452A (en) | 1971-04-28 | 1973-11-27 | Gen Electric | Platinum complexes of unsaturated siloxanes and platinum containing organopolysiloxanes |
| GB1476314A (en) | 1973-06-23 | 1977-06-10 | Dow Corning Ltd | Coating process |
| GB2013207B (en) | 1977-11-14 | 1982-10-27 | Spencer J L | Hydrosilylation catalysts |
| US4550152A (en) | 1983-10-28 | 1985-10-29 | General Electric Company | Nickel complex catalyst for hydrosilation reactions |
| US4578497A (en) | 1984-11-30 | 1986-03-25 | Gulf Research & Development Company | Tetraalkylsilane synthetic fluids |
| US4572791A (en) | 1984-12-06 | 1986-02-25 | Gulf Research & Development Company | Production of saturated and unsaturated silahydrocarbon mixtures using rhodium catalyst, and to products produced thereby |
| US4729821A (en) | 1986-11-03 | 1988-03-08 | Board Of Regents, The University Of Texas System | In situ activation of catalysts by applied electrical potentials |
| US4788312A (en) | 1988-03-16 | 1988-11-29 | Technolube Division Lubricating Specialties Co. | Trisilahydrocarbon lubricants |
| FR2641785B1 (en) | 1989-01-19 | 1992-07-31 | Essilor Int | OXYGEN PERMEABLE TRANSPARENT POLYMER COMPOSITION FOR RIGID TYPE CONTACT LENSES |
| US5026893A (en) | 1990-06-11 | 1991-06-25 | Lubricating Specialties Company | Polysilahydrocarbon lubricants |
| JPH06503592A (en) | 1990-12-13 | 1994-04-21 | ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー | Radiation-activated hydrosilation reaction |
| CA2080153A1 (en) | 1991-11-29 | 1993-05-30 | Chris A. Sumpter | Heat curable organopolysiloxane compositions, preformed latent platinum catalysts, and methods for making |
| JPH05295269A (en) | 1991-11-29 | 1993-11-09 | General Electric Co <Ge> | Heat-curable organopolysiloxane composition, preformed latent platinum catalyst, and preparation thereof |
| US5736480A (en) * | 1994-02-22 | 1998-04-07 | California Institute Of Technology | Supported phase chiral sulfonated BINAP catalyst solubilized in alcohol and method of asymmetric hydrogenation |
| US5880241A (en) | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
| US5691435A (en) | 1996-01-25 | 1997-11-25 | Wacker-Chemie Gmbh | Crosslinkable compositions |
| US6417305B2 (en) | 1996-12-17 | 2002-07-09 | E. I. Du Pont De Nemours And Company | Oligomerization of ethylene |
| US6214761B1 (en) | 1996-12-17 | 2001-04-10 | E. I. Du Pont De Nemours And Company | Iron catalyst for the polymerization of olefins |
| US6423848B2 (en) | 1996-12-17 | 2002-07-23 | E. I. Du Pont De Nemours And Company | Tridentate ligand |
| US6432862B1 (en) | 1996-12-17 | 2002-08-13 | E. I. Du Pont De Nemours And Company | Cobalt catalysts for the polymerization of olefins |
| US6451938B1 (en) * | 1997-02-25 | 2002-09-17 | Exxon Mobil Chemical Patents Inc. | Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands |
| US6103946A (en) | 1997-07-15 | 2000-08-15 | E. I. Du Pont De Nemours And Company | Manufacture of α-olefins |
| SK2712000A3 (en) | 1997-09-05 | 2001-07-10 | Bp Chem Int Ltd | Polymerisation catalysts |
| DE69918684T2 (en) | 1998-03-12 | 2004-12-02 | Bp Chemicals Ltd. | polymerization catalysts |
| EP1062255B1 (en) | 1998-03-12 | 2003-07-02 | BP Chemicals Limited | Homopolymer of ethylene |
| ID27209A (en) | 1998-03-12 | 2001-03-08 | Bp Chem Int Ltd | POLYMERIZATION CATALYSTS |
| US6297338B1 (en) | 1998-03-30 | 2001-10-02 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
| US7906451B2 (en) | 1998-03-30 | 2011-03-15 | E.I. Du Pont De Nemours And Company | Mixed polymerization catalyst component for polymerizing olefins |
| DE19856115A1 (en) | 1998-12-04 | 2000-06-21 | Wacker Chemie Gmbh | Siloxane copolymers containing alkenyl groups |
| US6620895B1 (en) | 1999-03-22 | 2003-09-16 | E. I. Du Pont De Nemours And Company | Processing polyethylenes |
| US6281303B1 (en) | 1999-07-27 | 2001-08-28 | Eastman Chemical Company | Olefin oligomerization and polymerization catalysts |
| US6458905B1 (en) | 1999-08-16 | 2002-10-01 | Phillips Petroleum Company | Complexes of pyridldiimines with vanadium and other transition metals, and their use as olefin oligomerization and polymerization catalysts |
| US6278011B1 (en) | 1999-08-30 | 2001-08-21 | The University Of Dayton | Polysilahydrocarbons as lubricants for aerospace application |
| ATE328057T1 (en) | 2001-04-30 | 2006-06-15 | Ciba Sc Holding Ag | USE OF METAL COMPLEX COMPOUNDS AS OXIDATION CATALYSTS |
| WO2003042131A1 (en) | 2001-11-15 | 2003-05-22 | Stichting Voor De Technische Wetenschappen | Hydrogenation catalyst and catalysed hydrogenation process |
| US7247687B2 (en) | 2002-07-17 | 2007-07-24 | Exxonmobil Chemical Patents Inc. | Late transition metal catalysts for olefin polymerization and oligomerization |
| US7317057B2 (en) * | 2004-03-17 | 2008-01-08 | Exxonmobil Chemical Patents Inc. | Catalyst composition and use thereof |
| US8062552B2 (en) | 2005-05-19 | 2011-11-22 | Brookhaven Science Associates, Llc | Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates |
| CN100378111C (en) | 2005-07-01 | 2008-04-02 | 中国科学院上海有机化学研究所 | Compound, synthetic method and application of organosilicon containing carbon-oxygen-ether linkage |
| US7268096B2 (en) | 2005-07-21 | 2007-09-11 | Chevron Phillips Chemical Company Lp | Diimine metal complexes, methods of synthesis, and methods of using in oligomerization and polymerization |
| CA2627466A1 (en) | 2005-10-26 | 2007-05-03 | Ciba Holding Inc. | Coloured particles for electrophoretic displays |
| DE102005057460A1 (en) | 2005-12-01 | 2007-06-06 | Wacker Chemie Ag | Crosslinkable to high-strength elastomers ionically and / or organometallic functionalized silicone polymers |
| US7429672B2 (en) | 2006-06-09 | 2008-09-30 | Momentive Performance Materials Inc. | Process for the direct synthesis of trialkoxysilane |
| US7696269B2 (en) | 2006-12-28 | 2010-04-13 | Momentive Performance Materials Inc. | Silated core polysulfides, their preparation and use in filled elastomer compositions |
| US10724903B2 (en) | 2008-05-23 | 2020-07-28 | Nanyang Technological University | Polymer encapsulated particles as surface enhanced Raman scattering probes |
| EP2407187A3 (en) | 2010-07-15 | 2012-06-20 | ECP Entwicklungsgesellschaft mbH | Blood pump for invasive application within the body of a patient |
| JP4958995B2 (en) * | 2010-08-27 | 2012-06-20 | キヤノン株式会社 | Electrophotographic photosensitive member, process cartridge, and electrophotographic apparatus |
| WO2012071360A1 (en) | 2010-11-24 | 2012-05-31 | Momentive Performance Materials Inc. | Metal - catalyzed mono - hydrosilylation of polyunsaturated compounds |
| CN103339135B (en) | 2010-11-24 | 2016-09-14 | 莫门蒂夫性能材料股份有限公司 | In-situ activation as the metal complex of hydrosilylation catalysts |
| EP2643335B1 (en) | 2010-11-24 | 2015-03-11 | Momentive Performance Materials Inc. | Hydrosilylation catalyst |
| WO2013043846A1 (en) | 2011-09-20 | 2013-03-28 | Dow Corning Corporation | Metal containing hydrosilylation catalysts and compositions containing the catalysts |
| EP2758417A2 (en) | 2011-09-20 | 2014-07-30 | Dow Corning Corporation | Cobalt containing hydrosilylation catalysts and compositions containing the catalysts |
| US9782763B2 (en) | 2011-12-14 | 2017-10-10 | Momentive Performance Materials Inc. | Non-precious metal-based hyrdosilylation catalysts exhibiting improved selectivity |
| US8927674B2 (en) | 2012-08-16 | 2015-01-06 | Princeton University | Dehydrogenative silylation and crosslinking using cobalt catalysts |
| US9447125B2 (en) | 2012-08-16 | 2016-09-20 | Momentive Performance Materials Inc. | Reusable homogeneous cobalt pyridine diimine catalysts for dehydrogenative silylation and tandem dehydrogenative-silylation-hydrogenation |
| US9371340B2 (en) | 2012-08-16 | 2016-06-21 | Momentive Performance Materials Inc. | Dehydrogenative silylation, hydrosilylation and crosslinking using cobalt catalysts |
| US9371339B2 (en) | 2013-05-06 | 2016-06-21 | Momentive Performance Materials Inc. | Saturated and unsaturated silahydrocarbons via iron and cobalt pyridine diimine catalyzed olefin silylation |
| US9890182B2 (en) | 2013-05-06 | 2018-02-13 | Momentive Performance Materials Inc. | Selective 1,2-hydrosilylation of terminally unsaturated 1,3-dienes using iron catalysts |
| WO2014186513A1 (en) | 2013-05-15 | 2014-11-20 | Momentive Performance Materials Inc. | Activation of metal salts with silylhydrides and their use in hydrosilylation reactions |
| WO2015023328A1 (en) | 2013-08-14 | 2015-02-19 | Momentive Performance Materials Inc. | Reusable homogeneous cobalt pyridine dimine catalysts for dehydrogenative silylation and tandem dehydrogenative-silylation-hydrogenation |
| JP6486925B2 (en) | 2013-11-19 | 2019-03-20 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Cobalt catalyst and its use for hydrosilylation and dehydrogenation silylation |
-
2014
- 2014-11-19 CN CN201480073588.1A patent/CN105916870A/en active Pending
- 2014-11-19 EP EP14863983.4A patent/EP3071552A1/en not_active Withdrawn
- 2014-11-19 JP JP2016532096A patent/JP2016540753A/en active Pending
- 2014-11-19 WO PCT/US2014/066422 patent/WO2015077344A1/en active Application Filing
- 2014-11-19 EP EP14815501.3A patent/EP3071586A1/en not_active Withdrawn
- 2014-11-19 US US14/547,726 patent/US9381506B2/en not_active Expired - Fee Related
- 2014-11-19 TW TW103140143A patent/TW201524602A/en unknown
- 2014-11-19 US US15/037,954 patent/US10112961B2/en active Active
- 2014-11-19 WO PCT/US2014/066356 patent/WO2015077306A1/en active Application Filing
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955555A (en) | 1996-12-17 | 1999-09-21 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene |
| US6657026B1 (en) | 1998-03-12 | 2003-12-02 | Bp Chemicals Limited | Polymerization catalysts |
| US7148304B2 (en) | 1998-03-12 | 2006-12-12 | Bp Chemicals Limited | Polymerization catalysts |
| US6461994B1 (en) | 1998-09-12 | 2002-10-08 | Bp Chemicals Limited | Polymerization catalyst |
| US7053020B2 (en) | 2002-09-25 | 2006-05-30 | Shell Oil Company | Catalyst systems for ethylene oligomerisation to linear alpha olefins |
| US7442819B2 (en) | 2004-07-09 | 2008-10-28 | E. I. Du Pont De Nemours And Company | Catalysts for olefin polymerization or oligomerization |
| US7507775B2 (en) | 2005-10-13 | 2009-03-24 | Momentive Performance Materials Inc. | Hydrolysis resistant organomodified disiloxane surfactants |
| US7259220B1 (en) | 2006-07-13 | 2007-08-21 | General Electric Company | Selective hydrosilylation method |
| US7326761B1 (en) | 2006-07-13 | 2008-02-05 | General Electric Company | Selective hydrosilylation method and product |
| US20110009565A1 (en) * | 2009-07-10 | 2011-01-13 | Delis Johannes G P | Hydrosilylation Catalysts |
| US8236915B2 (en) | 2009-07-10 | 2012-08-07 | Momentive Performance Materials Inc. | Hydrosilylation catalysts |
Non-Patent Citations (5)
| Title |
|---|
| BERGENS, S. H.; NOHEDA, P.; WHELAN, J.; BOSNICH, B., J. AM. CHEM. SOC., vol. 114, 1992, pages 2121 - 2128 |
| DI ZHU ET AL: "A Measure for [sigma]-Donor and [pi]-Acceptor Properties of Diiminepyridine-Type Ligands", ORGANOMETALLICS, vol. 27, no. 12, 1 June 2008 (2008-06-01), pages 2699 - 2705, XP055164740, ISSN: 0276-7333, DOI: 10.1021/om701160b * |
| INORG. CHEM., vol. 49, 2010, pages 6110 |
| JACS, vol. 132, 2010, pages 1676 |
| KNIJNENBURG Q ET AL: "Olefin hydrogenation using diimine pyridine complexes of Co and Rh", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, ELSEVIER, AMSTERDAM, NL, vol. 232, no. 1-2, 3 May 2005 (2005-05-03), pages 151 - 159, XP027658306, ISSN: 1381-1169, [retrieved on 20050503] * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018522946A (en) * | 2015-07-24 | 2018-08-16 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Dehydrogenated silylation, hydrosilylation and crosslinking using pyridinediimine cobalt carboxylate catalyst |
| US11760839B2 (en) | 2019-11-26 | 2023-09-19 | Dow Silicones Corporation | Processes for making polysiloxazanes and using same for producing amino-functional polyorganosiloxanes |
| CN113201018A (en) * | 2021-04-30 | 2021-08-03 | 安徽大学 | Mn (II) complex with AIE property and living cell mitochondria targeting function and preparation method and application thereof |
| CN113201018B (en) * | 2021-04-30 | 2023-06-27 | 安徽大学 | Mn (II) complex with AIE property and targeted living cell mitochondrial function, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20150141648A1 (en) | 2015-05-21 |
| EP3071552A1 (en) | 2016-09-28 |
| TW201524602A (en) | 2015-07-01 |
| US10112961B2 (en) | 2018-10-30 |
| US9381506B2 (en) | 2016-07-05 |
| US20160297838A1 (en) | 2016-10-13 |
| CN105916870A (en) | 2016-08-31 |
| WO2015077344A1 (en) | 2015-05-28 |
| JP2016540753A (en) | 2016-12-28 |
| EP3071586A1 (en) | 2016-09-28 |
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