WO2003011455A1 - Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts - Google Patents
Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts Download PDFInfo
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- WO2003011455A1 WO2003011455A1 PCT/US2002/019167 US0219167W WO03011455A1 WO 2003011455 A1 WO2003011455 A1 WO 2003011455A1 US 0219167 W US0219167 W US 0219167W WO 03011455 A1 WO03011455 A1 WO 03011455A1
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- Prior art keywords
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- substituted
- alkyl
- unsubstituted
- compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000005649 metathesis reaction Methods 0.000 title claims abstract description 27
- 229910052762 osmium Inorganic materials 0.000 title claims abstract description 23
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 23
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims description 23
- 239000002184 metal Substances 0.000 title claims description 18
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims description 15
- 239000003446 ligand Substances 0.000 claims abstract description 139
- -1 C2-C20 alkynyl Chemical group 0.000 claims abstract description 68
- 125000003118 aryl group Chemical group 0.000 claims abstract description 60
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000001424 substituent group Chemical group 0.000 claims abstract description 37
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 31
- 230000007935 neutral effect Effects 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 26
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 21
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims abstract description 18
- 150000001408 amides Chemical class 0.000 claims abstract description 16
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000003568 thioethers Chemical class 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 150000002466 imines Chemical class 0.000 claims abstract description 13
- 125000000129 anionic group Chemical group 0.000 claims abstract description 12
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 11
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims abstract description 10
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 155
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 112
- 230000015572 biosynthetic process Effects 0.000 claims description 81
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 79
- 238000003786 synthesis reaction Methods 0.000 claims description 79
- 239000000203 mixture Substances 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 40
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 25
- 150000001336 alkenes Chemical class 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 150000002431 hydrogen Chemical group 0.000 claims description 14
- 150000003222 pyridines Chemical class 0.000 claims description 14
- 150000004820 halides Chemical group 0.000 claims description 13
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 10
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 150000002390 heteroarenes Chemical class 0.000 claims description 10
- 150000003003 phosphines Chemical class 0.000 claims description 10
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 229920002554 vinyl polymer Chemical group 0.000 claims description 7
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 6
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 6
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 6
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 6
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 6
- 125000004414 alkyl thio group Chemical group 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 6
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 5
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 125000003944 tolyl group Chemical group 0.000 claims description 5
- 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 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 claims description 3
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 claims description 3
- HKOAFLAGUQUJQG-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine Chemical compound N1=CC=CN=C1C1=NC=CC=N1 HKOAFLAGUQUJQG-UHFFFAOYSA-N 0.000 claims description 3
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 229910000074 antimony hydride Inorganic materials 0.000 claims description 3
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005228 aryl sulfonate group Chemical group 0.000 claims description 3
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 3
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 claims description 3
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 125000005538 phosphinite group Chemical group 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical compound [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 239000002367 phosphate rock Substances 0.000 claims 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 19
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract description 16
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 11
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001299 aldehydes Chemical class 0.000 abstract description 11
- 150000001718 carbodiimides Chemical class 0.000 abstract description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 11
- 239000012948 isocyanate Substances 0.000 abstract description 11
- 150000002513 isocyanates Chemical class 0.000 abstract description 11
- 150000002576 ketones Chemical class 0.000 abstract description 11
- LJDZFAPLPVPTBD-UHFFFAOYSA-N nitroformic acid Chemical compound OC(=O)[N+]([O-])=O LJDZFAPLPVPTBD-UHFFFAOYSA-N 0.000 abstract description 11
- 150000003573 thiols Chemical class 0.000 abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 8
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 8
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract description 8
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002081 enamines Chemical class 0.000 abstract description 8
- 150000003949 imides Chemical class 0.000 abstract description 8
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 abstract description 8
- 150000003457 sulfones Chemical class 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 abstract 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 abstract 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 340
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 218
- 239000000460 chlorine Substances 0.000 description 166
- 239000011541 reaction mixture Substances 0.000 description 123
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 120
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 100
- 238000006243 chemical reaction Methods 0.000 description 89
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 77
- 239000000843 powder Substances 0.000 description 63
- 229910052786 argon Inorganic materials 0.000 description 60
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 46
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 33
- 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 32
- 239000007787 solid Substances 0.000 description 30
- 230000008859 change Effects 0.000 description 29
- 239000002244 precipitate Substances 0.000 description 28
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 23
- MITDXNUXOAYFGC-UHFFFAOYSA-N 1-prop-2-ynylbenzimidazole Chemical compound C1=CC=C2N(CC#C)C=NC2=C1 MITDXNUXOAYFGC-UHFFFAOYSA-N 0.000 description 21
- 239000000376 reactant Substances 0.000 description 21
- 125000003710 aryl alkyl group Chemical group 0.000 description 19
- 125000001072 heteroaryl group Chemical group 0.000 description 19
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 19
- 238000004458 analytical method Methods 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 18
- 125000004475 heteroaralkyl group Chemical group 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 16
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 16
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 16
- KMRASZKMNHTING-UHFFFAOYSA-N 4-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CCCCCC)C2 KMRASZKMNHTING-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- DNBWGFKLIBQQSL-UHFFFAOYSA-N n-methyl-1-pyridin-4-ylmethanamine Chemical compound CNCC1=CC=NC=C1 DNBWGFKLIBQQSL-UHFFFAOYSA-N 0.000 description 12
- 125000000753 cycloalkyl group Chemical group 0.000 description 11
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 11
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 10
- 125000004366 heterocycloalkenyl group Chemical group 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 8
- 241000894007 species Species 0.000 description 8
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 7
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- 150000001555 benzenes Chemical class 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical class C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 150000001925 cycloalkenes Chemical class 0.000 description 1
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- 125000001162 cycloheptenyl group Chemical class C1(=CCCCCC1)* 0.000 description 1
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- 125000002704 decyl 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])* 0.000 description 1
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- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- RIZMRRKBZQXFOY-UHFFFAOYSA-N ethion Chemical compound CCOP(=S)(OCC)SCSP(=S)(OCC)OCC RIZMRRKBZQXFOY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- LJKNRSBEKUSSIE-UHFFFAOYSA-N hept-2-ene Chemical compound [CH2]CCCC=CC LJKNRSBEKUSSIE-UHFFFAOYSA-N 0.000 description 1
- JAGYXYUAYDLKNO-UHFFFAOYSA-N hepta-2,5-diene Chemical compound CC=CCC=CC JAGYXYUAYDLKNO-UHFFFAOYSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ARIRIZBKMKMEBD-UHFFFAOYSA-N n-hydroxy-2-[4-(4-phenoxy-benzenesulfonyl)-tetrahydro-pyran-4-yl]-acetamide Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1S(=O)(=O)C1(CC(=O)NO)CCOCC1 ARIRIZBKMKMEBD-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000006772 olefination reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000010452 phosphate Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
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- 238000010094 polymer processing Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 238000001175 rotational moulding Methods 0.000 description 1
- 238000005872 self-metathesis reaction Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229920006250 telechelic polymer Polymers 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- SWUFZSQHKFLQTM-UHFFFAOYSA-N tripyrazol-1-yl borate Chemical compound C1=CC=NN1OB(ON1N=CC=C1)ON1C=CC=N1 SWUFZSQHKFLQTM-UHFFFAOYSA-N 0.000 description 1
- 239000004762 twaron Substances 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2269—Heterocyclic carbenes
- B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
- C07C6/06—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond at a cyclic carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/002—Osmium 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
-
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- 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
- B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
- B01J2231/54—Metathesis reactions, e.g. olefin metathesis
- B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/466—Osmium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/825—Osmium
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Definitions
- the present invention relates to novel hexacoordinated metathesis catalysts and to methods for making and using the same.
- the inventive catalysts are of the formula
- M is ruthenium or osmium
- X and X 1 are the same or different and are each independently an anionic ligand
- L, L 1' and L 2 are the same or different and are each independently a neutral electron donor ligand; and, R and R 1 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, Ci-C 2 o carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C ! -C 2 o alkylthio, Ci-C 2 o alkylsulfonyl, C ! -C 2 o alkylsulfinyl, and silyl.
- each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci-Cio alkyl, C ⁇ -C 10 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -C 5 alkyl, -Cs alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate. halogen, alcohol, sulfonic acid, phospbine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
- L and L are pyridine and L is a phosphine or an N- heterocyclic carbene ligand.
- N-heterocyclic carbene ligands include:
- R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C -C 20 alkynyloxy, aryloxy, C -C 20 alkoxycarbonyl, C 1 -C 0 alkylthio, C 1 -C 20 alkylsulfonyl. C 1 -C 20 alkylsulfmyl and silyl.
- each of the R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 and R 1 substituent group may be substituted with one or more moieties selected from the group consisting of -Cio alkyl, C 1 - 0 alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -Cs alkyl, CrC 5 alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide. acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
- NHC ligand to the hexacoordinated ruthenium or osmium catalysts has been found to dramatically improve the properties of these complexes. Because the NHC-based hexacoordinated complexes are extremely active, the amount of catalysts that is required is significantly reduced.
- the present invention generally relates to ruthenium and osmium carbene catalysts for use in olefin metathesis reactions. More particularly, the present invention relates to hexacoordinated ruthenium and osmium carbene catalysts and to methods for making and using the same.
- the terms "catalyst” and “complex” herein are used interchangeably.
- M is ruthemum or osmium
- X and X 1 are each independently any anionic ligand
- L and L 1 are each independently any neutral electron donor ligand; R and R 1 are the same or different and are each independently hydrogen or a substituent selected from the group consisting of -C 2 o alkyl, C 2 -C 20 alkenyl, C 2 -C 0 alkynyl, aryl, -C2 0 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 0 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, C 1 -C 20 alkylthio, C 1 -C 0 alkylsulfonyl, C 1 -C 20 alkylsulfinyl, and silyl.
- each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci- o alkyl, Ci-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a Ci-C 5 alkyl, -C 5 alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulf nic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
- the catalysts of the present invention are similar in that they are Ru or Os complexes; however, in these complexes, the metal is formally in the +2 oxidation state, and has an electron count of 18 and are hexacoordinated.
- These catalysts are of the general formula:
- M is ruthenium or osmium
- X and X 1 are the same or different and are each independently any anionic ligand
- L. L 1' , and L 2 are the same or different and are each independently any neutral electron donor ligand;
- R and R 1 are the same or different and are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 0 alkyl, C 2 -C 20 alkenyl, C 2 -C 0 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 0 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, -C20 alkylsulfinyl, and silyl.
- each of the R or R 1 substituent group may be substituted with one or more moieties selected from the group consisting of Ci-Cio alkyl, Ci-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a -C 5 alkyl, -Cs alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide, acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
- the hexacoordinated complex provides several advantages over the well-known pentacoordinated complexes.
- the hexacoordinated complexes have greater air stability in the solid state because they are coordinatively saturated. Due to the lability of the additional ligand, e.g. pyridines, the complexes initiate faster than the phosphine based pentacoordinated species. Slow initiation means that only a small amount of complex is actually catalystically active thereby wasting much of the added complex. With faster initiators, catalyst loading is lowered.
- the pentacoordinated benzylidene with triphenylphosphme as its phosphine ligand can be prepared in higher yield and with greater purity using the hexacoordinated complex.
- the pentacoordinated benzylidene with P(/?-CF 3 C 6 H 4 ) 3 as its phosphine ligand is inaccessible through existing routes. Without being bound by theory, it is believe that this is because it would require the substitution of a stronger donor ligand with a weaker donor ligand. Substitution of the anionic ligands of the hexacoordinated complexes is much more rapid than with the corresponding pentacoordinated species (e.g. phosphine bound). Without being bound by theory, it is believed that this results from the requirement of ligand dissociation before anionic ligand substitution. Thus complexes with fast dissociation of their neutral electron donor ligands will undergo faster substitution.
- the catalysts of the invention are also useful for ring-opening metathesis polymerization (ROMP), ring-closing metathesis (RCM), ADMET. and cross- metathesis.
- ROMP ring-opening metathesis polymerization
- RCM ring-closing metathesis
- ADMET ADMET.
- cross- metathesis The synthesis and polymerization of olefins via these metathesis reactions can be found in, for example, U.S. Application Nos. 09/891,144 entitled: "Synthesis of Functionalized and Unfunctionalized Olefins, filed June 25, 2001, and U.S. Application No. 09/491,800, the contents of each of which are incorporated herein by reference.
- Preferred embodiments of the catalysts of the invention possess at least one NHC ligand attached to the metal center, as illustrated by the following general formula:
- the R substituent is hydrogen and the R 1 substituent is selected from the group consisting of -C 20 alkyl, C 2 -C 20 alkenyl, and aryl.
- the R 1 substituent is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of -C 5 alkyl, -C 5 alkoxy, phenyl, and a functional group.
- R 1 is phenyl or vinyl substituted with one or more moieties selected from the group consisting of chloride, bromide, iodide, fluoride, -NO 2 , - NMe 2 , methyl, methoxy and phenyl.
- the catalyst is of the general formula:
- R' and R" are preferably independently hydrogen or phenyl but can be selected from any of the groups listed for R or R 1 .
- X and X 1 are each independently hydrogen, halide, or one of the following groups: C ⁇ -C 2 o alkyl, aryl, C1-C2 0 alkoxide, aryloxide, C 3 -C 20 alkyldiketonate, aryldiketonate, C 1 -C 20 carboxylate, arylsulfonate, C o alkylsulfonate, -C2 0 alkylthio, C C 2 o alkylsulfonyl, or C C 2 o alkylsulfinyl.
- X and X 1 may be substituted with one or more moieties selected from the group consisting of -Cio alkyl, d-Cio alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from halogen, C C 5 alkyl, Ci-C 5 alkoxy, and phenyl.
- X and X 1 are halide, benzoate, Q-Cs carboxylate, -C 5 alkyl, phenoxy, -C 5 alkoxy, -Cs alkylthio, aryl, and C ⁇ - C 5 alkyl sulfonate.
- X and X 1 are each halide, CF 3 CO 2 , CH 3 CO 2 . CFH 2 CO 2 , (CH 3 ) 3 CO, (CF 3 ) 2 (CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate.
- X and X 1 are each chloride.
- L, L , L and L may be any appropriate monodentate or multidentate neutral electron donor ligands.
- Multidentate neutral electron donor ligands include bidentate, tridentate, or tetradentate neutral electron donor ligands, for example.
- L, L 1 , L 1' and L 2 are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphorate, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether, or any derivatives therefrom. At least one
- L, L , L and L may also be an N-heterocyclic carbene ligand.
- Preferred embodiments include complexes where both L and L are either the same or different NHC ligands.
- At least one of L, L 1 , L 1' and L 2 is a phosphine of the formula PR 3 R 4 R 5 , where R 3 , R 4 , and R 5 are each independently aryl or Ci-do alkyl, particularly primary alkyl, secondary alkyl or cycloalkyl.
- at least one of L, L 1 , L 1 ' and L 2 is each selected from the group consisting of -P(cyclohexyl) 3 , -P(cyclopentyl) 3 , -P(isopropyl) 3 , and -P(phenyl) 3 .
- L, L 1 , L 1 and L 2 are each NHC ligand.
- L is an NHC
- L 1 is P(cyclohexyl) 3 or -P(cyclopentyl) 3
- L 1 and L 2 are each heterocyclic ligands, optionally aromatic, or together form a bidenatate ligand.
- L 1 and L 2 are each independently pyridine or a pyridine derivative.
- NHC ligands examples include ligands of the general formulas:
- R, R 1 , R', R", R 6 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently hydrogen or a substituent selected from the group consisting of d-C 20 alkyl, C 2 -C 2 o alkenyl, C 2 - C 20 alkynyl, aryl, C 1 -C 20 carboxylate, C 1 -C 2 o alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 2 o alkynyloxy, aryloxy, C 2 -C 0 alkoxycarbonyl, C ⁇ -C 20 alkylthio, C 1 -C 20 alkylsulfonyl, C 1 -C 20 alkylsulfmyl, and silyl.
- each of the R, R 1 R 6 , R 7 , R 8 , R 9 , R 10 , and R 1 substituent group may be substituted with one or more moieties selected from the group consisting of d-do alkyl, Ci-do alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a Ci-Cs alkyl, C1-C 5 alkoxy, and phenyl.
- any of the catalyst ligands may further include one or more functional groups.
- Suitable functional groups include but are not limited to: hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, halogen, alcohol, sulfonic acid, phosphine, imide. acetal, ketal, boronate, cyano, cyanohydrin, hydrazine, enamine, sulfone, sulfide, and sulfenyl.
- R 6 , R 7 , R 8 and R 9 are independently selected from the group consisting of hydrogen, phenyl, or together form a cycloalkyl or an aryl optionally substituted with one or more moieties selected from the group consisting of Ci-do alkyl, d-do alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen; and R 10 and R 11 are each is independently d- do alkyl or aryl optionally substituted with d-C 5 alkyl, d-C 5 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether
- R and R are both hydrogen or phenyl, or R and R together form a cycloalkyl group;
- R 8 and R 9 are hydrogen and R 10 and R 11 are each either substituted or unsubstituted aryl.
- R 10 and R 11 are the same and each is independently of the formula:
- R 12 , R 13 , and R 14 are each independently hydrogen, d-do alkyl, d-do alkoxy, aryl, or a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen, hi especially preferred embodiments, R 12 , R 13 , and R 1 are each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, hydroxyl, and halogen. In the most preferred embodiments, R 12 , R 13 , and R 14 are the same and are each methyl.
- R , R , R , and R are each independently hydrogen or a substituent selected from the group consisting of C 1 -C 0 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, C ⁇ -C 20 carboxylate, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, d-C 2 o alkylthio, d-C 20 alkylsulfonyl and d-C 2 o alkylsulfinyl.
- Lnidazolidine ligands are also referred to as imidizol-2-ylidene ligands.
- neutral electron donor ligands include ligands which are derived, for example, from unsubstituted or substituted heteroarenes such as furan, thiophene, pyrrole, pyridine, bipyridine, picolylimine, gamma-pyran, gamma-thiopyran, phenanthroline, pyrimidine, bipyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, dithiazole, isoxazole, isothiazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bis, bis
- heteroaralkyl, aralkenyl and heteroaralkenyl in turn are unsubstituted or substituted by one of the above-mentioned substituents; and y is 1 and M is a monovalent metal or y is 1/2 and M is a divalent metal.
- metal and corresponding cations refer to an alkali metal, for example Li, Na or K, an alkaline earth metal, for example Mg, Ca or Sr, or Mn, Fe, Zn or Ag, and corresponding cations.
- Lithium, sodium and potassium ions, with their salts, are preferred.
- NH 2 monoamino, diamino, carbamide, carbamate, carbohydrazide, sulfonamide, sulfohydrazide and aminocarbonylamide correspond preferably to a group R 8 C(O)(NH) p N(R 9 )--, -C(O)(NH) p NR 8 R 9 , R 8 OC(O)(NH) p N(R 9 ) ⁇ , R 8 R 40 NC(O)(NH)p N(R 9 ) ⁇ , -OC(O)(NH) p R 8 R 9 , --NO C O) ⁇ H) P NR 8 R 9 , R 8 S(O) 2 (NH) P N(R 9 )-; - S(O) 2 (NH) p NR 8 R 9 ; R 8 R 40 NS(O) 2 N(R 9 ) ⁇ or --NR ⁇ O) 2 NR 8 R 9 , in which R 8 , R 9 and io independently of one another are
- the sulfonyl substituent is, for example, of the formula R 10 --SO 2 -- in which R 10 is d- C t2 alkyl, C -Ci 2 cycloalkyl, d-C ⁇ heterocycloalkyl, C 6 -do aryl, C 5 -C 9 heteroaryl, C 7 -C ⁇ aralkyl or C 6 -C 10 heteroaralkyl which are unsubstituted or substituted by one or more substituents selected from the group consisting of OH, halogen, C(O)OR sl , OC(O)R s4 , C(O)R S2 , nitro, NH 2 , cyano, SO 3 Z y , OSO 3 Z y , NR 20 SO 3 Z y , C C 12 alkyl, C 2 -C 12 alkenyl, d-C 1 alkoxy, C 3 -C 12 cycloalkyl, C 3 -C 12
- a more preferred group of compounds is formed when L and L independently of one another are pyridyl which is unsubstituted or substituted by one or more substituents from the group consisting of d-C 12 alkyl, C 2 -C ⁇ heterocycloalkyl, C 5 -C heteroaryl, halogen, monoamino, diamino and -C(O)H. Examples are
- Examples are:
- L 2 and L 1 are each independently selected from the group consisting of:
- R is selected from the group consisting of hydrogen or a substituent selected from the group consisting of d-C 2 o alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, aryl, d-C 20 carboxylate, Ci-C 20 alkoxy, C 2 -C 20 alkenyloxy, d-do alkynyloxy, aryloxy, C 2 -C 20 alkoxycarbonyl, d-C 2 o alkylthio, Ci-C 20 alkylsulfonyl, d-C 2 o alkylsulfinyl, and silyl.
- the R group may be substituted with one or more moieties selected from the group consisting of d-C 10 alkyl, d-do alkoxy, and aryl which in turn may each be further substituted with one or more groups selected from a halogen, a d-C 5 alkyl, d-C 5 alkoxy, and phenyl.
- any of the heterocycles may further include one or more functional groups.
- R is selected from the group consisting of d-C 2 o alkyl, aryl, ether, amine, halide, nitro, ester and pyridyl.
- complexes 1-4 and 44-48 are used to make the preferred embodiments 5- 29 and 49-83 of the inventive complex:
- L is an NHC, preferably an imidazolidine ligand, and L and L ' are pyridines.
- the complexes can also be of the formulae:
- M and M' are independently selected from the group consisting of ruthenium and osmium, X, X 1 , L 2 , L 1 , R and R 1 are as previously defined, X and X are substituted or unsubstituted and are independently selected from the group from which X and X 1 are selected, R and R 1 are substituted or unsubstituted and are independently selected from the group from which R and R 1 are selected, L 1 is selected from the group from which L 1 is selected, L 2 is any bidentate, neutral electron donor ligand, and L 3 is any tetradentate, neutral electron donor ligand.
- one aspect of the invention is a catalyst of the general structure:
- the starting complexes may be selected from the following:
- cumulated pentacoordinated complexes for example, those seen in complexes 1-4 (a, b), in the inventive process will produce inventive cumulated hexacoordinated complexes.
- the cumulated complexes corresponding to complex 5 is as follows:
- compounds 6-29 may also have corresponding cumulated complexes.
- At least one of L, L 1 , L 1 , L 2 , X, X 1 , R and R 1 may be linked to at least one other of L, L 1 , L 1 , L 2 , X, X 1 , R and R 1 to form a bidentate or multidentate ligand array.
- the inventive catalysts are made by contacting excess neutral electron donor ligand, such as a pyridine, with the previously described penta-coordinated metal carbene catalyst complex of the formula:
- Ligands L and L may be the same compound, for example, pyridines (when excess pyridine is used), or may together form a bidentate ligand.
- L 1 and L 1 may be the same, in which case, the pentacoordinated
- the inventive complex may also be a cumulated carbene complex of the general formulas:
- the inventive hexacoordinated catalyst complexes provide synthetic utility and utility in catalytic reactions. Without being bound by theory, these complexes contain substitutionally labile ligands, for example, pyridine and chloride ligands, and serve as a versatile starting material for the synthesis of new ruthenium metal carbene complexes.
- the chloride ligands are more labile than in the corresponding pentacoordinated phosphine-based complexes.
- X and X are any anionic ligand.
- X and X 1 are selected from the group consisting of chloride, bromide, iodide, Tp, alkoxide, amide, and thiolate.
- the pyridine ligands are more labile than the phosphines in the corresponding pentacoordinated phosphine-
- L, L , L , and L can be any neutral electron donor ligands, including a NHC ligand. Depending on the size of the ligand, one or two neutral ligands (in addition to the NHC) may bind to the metal center.
- inventive catalyst complexes may be used in both metathesis reactions or the formation of an NEC ligand based complex.
- the hexacoordinated complex can lose a neutral electron donor ligand to produce the pentacoordinated catalyst complex.
- the reaction may also proceed the other way to produce a hexacoordinated complex in the presence of excess L 2 .
- the pentacoordinated complex may also lose the L 1 ligand to form the metathesis active tetracoordinated species (Scheme 5):
- the L 1 ligand may also attach to a tetracoordinated species to form the pentacoordinated complex.
- the tetracoordinated species may then initiate polymerization when in the presence of an olefin, as shown in Scheme 6, or may form the NHC-ligand based pentacoordinated complex when in the presence of a protected NHC-ligand (Scheme 7):
- NHC- A-B indicates generally the protected form of a N- Heterocyclic Carbene (NHC).
- the protected NHC- A-B may be of an unsaturated variety, such as
- A is preferably H, Si, Sn, Li, Na, MgX 3 and acyl, wherein X 3 is any halogen, and B may be selected from the group consisting of CC1 3 ; CH 2 SO 2 Ph;
- R is selected from the group consisting of Me, C 2 H 5 , i-C 3 H 7 , CH 2 CMe 3 , CMe 3 , C 6 H n (cyclohexyl), CH 2 Ph, CH 2 norbornyl, CH 2 norbornenyl, C 6 H 5 , 2,4,6-(CH 3 ) 3 C 6 H 2 (mesityl), 2,6-i-Pr 2 C 6 H 2 , 4-Me-C 6 IL; (tolyl), 4-Cl-C 6 H 4 ; and wherein R 22 and R 23 are independently selected from the group consisting of Me, C 2 H 5 , i-C 3 H 7 , CH 2 CMe 3 , CMe 3 , C 6 H n (cyclohexyl), CH 2 Ph, CH 2 norbornyl, CH 2 norbornenyl, C 6 H 5 , 2,4,6-(CH 3 ) 3 C 6 H
- This approach relates to the thermal generation of a NHC ligand from a stable (protected) NHC derivative with a release of a quantity of A-B.
- One of the more preferred methods to generate a reactive NHC ligand is to employ a stable carbene precursor where the A-B compound is also a reactive NHC ligand.
- a detailed description of the protected NHC and related methods of synthesis and use canbe seen m U.S. Patent Application Nos. 10/107,531 and No. 10/138,188 the contents of each of which are inco ⁇ orated herein by reference.
- the following structure for the sImesHCCl 3 shows a preferred embodiment of a protected NHC ligand for use with the inventive hexacoordinated complexes:
- the NHC ligand based pentacoordinated complex may then lose the L ligand to form the metathesis active tetracoordinated species and proceed to initiate the polymerization reaction in the presence of an olefin (Scheme 8):
- the hexacoordinated complex can undergo a ligand exchange such that the NHC replaces another neutral electron donor ligand resulting in an NHC ligand based hexacoordinated complex (Scheme 9):
- Crystals suitable for X-ray crystal structure determination were grown by vapor diffusion of pentane into a saturated benzene solution of 31 at room temperature.
- the collection and refinement parameters for the crystallographic analysis are summarized in Table 1.
- the Ru-C(38) (N-heterocyclic carbene) bond length of 2.033(4) A is approximately 0.05 A shorter than that in complex 1, which is likely due to the relatively small size and moderate trans influence of pyridine relative to PCy 3 .
- the 0.15 A difference in the Ru-C(l) and Ru-C(38) bond distances highlights the covalent nature of the former and the dative nature of the latter ruthenium-carbene bond.
- the para-substituted triphenylphosphme derivatives 35, 36 and 37 (containing para substituents CF 3 , CI, and OMe, respectively) can be prepared using the inventive method.
- the triarylphosphine ruthenium complexes 32, 35-37 are valuable catalysts as they are almost 2 orders of magnitude more active for olef ⁇ n metathesis reactions than the parent complex 1.
- the electron-poor phosphine P(C 6 F 6 ) 3 shows no reaction with 31, even under forcing conditions.
- the chlorine ligands of 31 are also substantially labile relative to those in the parent complex 1.
- the reaction between 1 and Nal takes approximately 8 hours to reach completion under identical conditions.
- 1H NMR spectroscopy reveals that the diiodide complex 38 contains only one pyridine ligand, while the analogous dichloride species 31 coordinates 2 equiv. of pyridine.
- the relatively large size of the iodide ligands and the lower electrophilicity at the metal center in 38 are both believed to contribute to the formation of a five-coordinate complex in this system.
- this ligand substitution proceeds by an associative mechanism.
- Complex 31 reacts readily with phosphines, providing access to new complexes discussed herein.
- Complex 31 also undergoes reaction with KO t - Bu, Nal, and KTp to provide new four-, five-, and six- coordinate ruthenium benzylidenes.
- the inventive methodology is useful for facilitating the development of new ruthenium olefin metathesis catalysts containing structurally diverse ligand arrays.
- inventive complexes are useful in olefin metathesis reactions, particularly for polymerization reactions.
- These catalysts can be used in various metathesis reactions, including but not limited to, ring-opening metathesis polymerization of strained and unstrained cyclic olefins, ring-closing metathesis of acyclic dienes, acyclic diene metathesis polymerization ("ADMET"), self- and cross-metathesis reactions, alkyne polymerization, carbonyl olefination, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
- ring-opening metathesis polymerization of strained and unstrained cyclic olefins ring-closing metathesis of acyclic dienes
- ADMET acyclic diene metathesis polymerization
- self- and cross-metathesis reactions self- and cross-metathesis reactions, alkyne polymerization, carbonyl ole
- the most preferred olefin monomer for use in the invention is substituted or unsubstituted dicyclopentadiene (DCPD).
- DCPD dicyclopentadiene
- Various DCPD suppliers and purities may be used such as Lyondell 108 (94.6% purity), Veliscol UHP (99+% purity), B.F. Goodrich Ultrene ® (97% and 99% purities), and Hitachi (99+% purity).
- olefin monomers include other cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclooctadiene (COD; DuPont); cyclooctene (COE, Alfa Aesar); cyclohexenylnorbornene (Shell); norbomene (Aldrich); norbomene dicarboxylic anhydride (nadic anhydride); norbornadiene (Elf Atochem); and substituted norbomenes including butyl norbomene, hexyl norbomene, octyl norbomene, decyl norbomene, and the like.
- the olefinic moieties include mono-or disubstituted olefins and cycloolefins containing between 3 and 200 carbons.
- metathesis-active olefinic moieties include substituted or unsubstituted cyclic or multicyclic olefins, for example, cyclopropenes, cyclobutenes, cycloheptenes, cyclooctenes, [2.2.1]bicycloheptenes, [2.2.2]bicyclooctenes, benzocyclobutenes, cyclopentenes, cyclopentadiene oligomers including trimers, tetramers, pentamers, and the like; cyclohexenes.
- compositions include frameworks in which one or more of the carbon atoms carry substituents derived from radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphoms, antimony, or boron.
- radical fragments including halogens, pseudohalogens, alkyl, aryl, acyl, carboxyl, alkoxy, alkyl- and arylthiolate, amino, aminoalkyl, and the like, or in which one or more carbon atoms have been replaced by, for example, silicon, oxygen, sulfur, nitrogen, phosphoms, antimony, or boron.
- the olefin may be substituted with one or more groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
- groups such as thiol, thioether, ketone, aldehyde, ester, ether, amine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, phosphate, phosphite, sulfate, sulfite, sulfonyl, carbodiimide, carboalkoxy, carbamate, halogen, or pseudohalogen.
- the olefin may be substituted with one or more groups such as C ⁇ -C 2 o alkyl, aryl, acyl, -C20 alkoxide, aryloxide, C 3 - C 20 alkyldiketonate, aryldiketonate, -C2 0 carboxylate, arylsulfonate, C 1 -C 20 alkylsulfonate, -C 20 alkylthio, arylthio, C 1 -C2 0 alkylsulfonyl, and -C20 alkylsulfinyl, Ci ⁇ o alkylphosphate, arylphosphate, wherein the moiety may be substituted or unsubstituted.
- groups such as C ⁇ -C 2 o alkyl, aryl, acyl, -C20 alkoxide, aryloxide, C 3 - C 20 alkyldiketonate, aryldiketonate,
- Examples of preferred polymerizable norbornene-type monomers include but are not limited to, norbomene (bicyclo[2.2.1]hept-2-ene), 5-methyl-2 -norbomene, ethylnorbornene, propylnorbornene, isopropylnorbornene, butylnorbornene, isobutylnorbornene, pentylnorbomene, hexylnorbornene, heptylnorbornene, octylnorbornene, decylnorbomene, dodecylnorbomene, octadecylnorbornene, p- tolylnorbornene, methyhdene norbomene, phenylnorbomene, ethylidenenorbomene, vinylnorbornene, exo-dicyclopentadiene
- indanylnorbornene i.e., l,4,4,9-tetrahydro-l,4- methanofluorene, the reaction product of CPD and indene
- 6,7, 10, 10-tetrahydro-7 10- methanofluoranthene
- l,4,4,9,9,10-hexahydro-9,10[ ,2']-benzeno-l,4-methanoanthracene endo,endo-5,6- dimethyl-2-norbomene, endo,exo-5,6-dimethyl-2-norbomene, exo,exo-5,6-dimethyl- 2-norbornene, 1 ,4,4,5,6,9, 10, 13 , 14, 14-decahydro- 1 ,4-methanobenzocyclododecene (i.e., reaction product of CPD and 1,5,9-cyclod
- olefin monomers may be used alone or mixed with each other in various combinations to adjust the properties of the olefin monomer composition.
- mixtures of cyclopentadiene dimer and trimers offer a reduced melting point and yield cured olefin copolymers with increased mechanical strength and stiffness relative to pure poly-DCPD.
- incorporation of COD, norbomene, or alkyl norbomene co-monomers tend to yield cured olefin copolymers that are relatively soft and rubbery.
- the resulting polyolefin compositions formed from the metathesis reactions are amenable to thermosetting and are tolerant of additives, stabilizers, rate modifiers, hardness and/or toughness modifiers, fillers and fibers including, but not limited to, carbon, glass, aramid (e.g., Kevlar ® and Twaron ® ), polyethylene (e.g., Spectra ® and Dyneema ® ), polyparaphenylene benzobisoxazole (e.g., Zylon ® ), polybenzamidazole (PBI), and hybrids thereof as well as other polymer fibers.
- aramid e.g., Kevlar ® and Twaron ®
- polyethylene e.g., Spectra ® and Dyneema ®
- polyparaphenylene benzobisoxazole e.g., Zylon ®
- polybenzamidazole PBI
- the metathesis reactions may optionally include formulation auxiliaries.
- auxiliaries include antistatics, antioxidants (primary antioxidants, secondary antioxidants, or mixtures thereof), ceramics, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fibers, lubricants, adhesion promoters, viscosity- increasing agents, and demolding enhancers.
- fillers for improving the optical physical, mechanical, and electrical properties include glass and quartz in the form of powders, beads, and fibers, metal and semi-metal oxides, carbonates (e.g. MgCO 3 , CaCO 3 ), dolomite, metal sulfates (e.g. gypsum and barite), natural and synthetic silicates (e.g. zeolites, wollastonite, and feldspars), carbon fibers, and plastics fibers or powders.
- the UN and oxidative resistance of the polyolefin compositions resulting from the metathesis reactions using the inventive carbene complex may be enhanced by the addition of various stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered amine light stabilizers or HALS), and UN light absorbers (e.g., hydroxy benzophenone absorbers, hydroxyphenylbenzotriazole absorbers, and the like), as described in U.S. Application No. 09/498,120, filed February 4, 2000, the contents of which are incorporated herein by reference.
- stabilizing additives such as primary antioxidants (e.g., sterically hindered phenols and the like), secondary antioxidants (e.g., organophosphites, thioesters, and the like), light stabilizers (e.g., hindered
- Exemplary primary antioxidants include, for example, 4,4'-methylenebis (2,6-di- tertiary-butylphenol) (Ethanox 702 ® ; Albemarle Corporation), l,3,5-trimethyl-2,4,6- tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (Ethanox 330 ® ; Albermarle Corporation), octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate (Irganox 1076 ® ; Ciba-Geigy), and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate)(Irganox ® 1010; Ciba-Geigy).
- Ethanox 702 ® Albemarle Corporation
- Exemplary secondary antioxidants include tris(2,4-ditert-butylphenyl)phosphite (Irgafos ® 168; Ciba-Geigy), l:ll(3,6,9-trioxaudecyl)bis(dodecylthio)propionate (Wingstay ® SN-1; Goodyear), and the like.
- Exemplary light stabilizers and absorbers include bis(l, 2,2,6,6- pentamethyl-4-piperidinyl)-[[3,5-bis(l,l-dimethylethyl)-4- hydroxyphenyl]methyl]butylmalonate (Tinuvin ® 144 HALS; Ciba-Geigy), 2-(2H- benzotriazol-2-yl)-4,6-ditertpentylphenol (Tinuvin ® 328 absorber; Ciba-Geigy), 2,4- di-tert-butyl-6-(5-chlorobenzotriazol-2-yl)phenyl (Tinuvin ® 327 absorber; Ciba- Geigy), 2-hydroxy-4-(octyloxy)benzophenone (Chimassorb ® 81 absorber; Ciba- Geigy), and the like.
- a suitable rate modifier such as, for example, triphenylphosphine (TPP), tricyclopentylphosphine, tricyclohexylphosphine, triisopropylphosphine, trialkylphosphites, triarylphosphites, mixed phosphites, or other Lewis base, as described in U.S. Patent No. 5,939,504 and U.S. Application No. 09/130,586, the contents of each of which are herein inco ⁇ orated by reference, may be added to the olefin monomer to retard or accelerate the rate of polymerization as required.
- TPP triphenylphosphine
- TPP triphenylphosphine
- tricyclopentylphosphine tricyclohexylphosphine
- triisopropylphosphine trialkylphosphites
- triarylphosphites triarylphosphites
- mixed phosphites or other Lewis base
- the resulting polyolefin compositions, and parts or articles of manufacture prepared therefrom may be processed in a variety of ways including, for example, Reaction Injection Molding (RIM), Resin Transfer Molding (RTM) and vacuum-assisted variants such as NARTM (Vacuum- Assisted RTM) and SCRIMP (Seemann Composite Resin Infusion Molding Process), open casting, rotational molding, centrifugal casting, filament winding, and mechanical machining.
- RIM Reaction Injection Molding
- RTM Resin Transfer Molding
- NARTM Vauum- Assisted RTM
- SCRIMP Seemann Composite Resin Infusion Molding Process
- the metathesis reactions may occur in the presence or absence of a solvent.
- solvents that can be used in the polymerization reaction include organic, protic, or aqueous solvents, which are preferably inert under the polymerization conditions.
- solvents include aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof.
- Preferred solvents include benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, water or mixtures thereof.
- the solvent is benzene, toluene, p-xylene, methylene chloride, dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, or mixtures thereof.
- the solvent is toluene, or a mixture of benzene and methylene chloride.
- the inventive complexes have a well-defined ligand environment that enables flexibility in modifying and fine-tuning the activity level, stability, solubility and ease of recovery of these catalysts.
- the solubility of the carbene compounds may be controlled by proper selection of either hydrophobic or hydrophilic ligands as is well known in the art.
- the desired solubility of the catalyst will largely be determined by the solubility of the reaction substrates and reaction products.
- the inventive metal carbene complexes have shown a high rate of initiation allowing for most, if not all, of the complex added to the reaction to be consumed. Thus, less catalyst is wasted in the metathesis reaction. In contrast, the previous pentacoordinated initiators had a higher amount of extractibles (i.e. unpolymerized monomer) remaining after the reaction concluded. The rate of propogation is also slowed by the presence of the two pyridine ligands. The high rate of initiation and low rate of propogation yields polymers with narrow polydisperities relative to those achieved with the earlier pentacoordinated complexes. Moreover, it was determined that heat increases the rate of the initiation.
- Thermal initiation of the pentacoordinated complexes can be seen in U.S. Patent No. 6,107,420, the contents of which are inco ⁇ orated herein by reference.
- the initiation and/or rate of the metathesis polymerization using the inventive catalysts is controlled by a method comprising contacting the inventive catalyst with an olefin and heating the reaction mixture.
- the T max for the thermal initiation of the inventive catalyst is significantly higher than the T ma ⁇ for the previous pentacoordinated catalysts.
- T max reduces the need for post cure. Additionally, even if peroxides or radicals are added to promote crosslinking, the degree of crosslinking in the part that uses the radical mechanism is increased in comparison to a part prepared using the previous pentacoordinated metathesis catalysts. Moreover, the half-life is dependent on the maximum temperature. Using the inventive catalysts, the half life is reduced substantially, and therefore less catalyst is needed, providing a significant commercial advantage. Without being bound by theory, the higher T max indicates that in a ROMP reaction, more rings are opened, and there is a better degree of cure. With a higher T ma ⁇ , the extractibles are almost to zero, indicating that almost every molecule that can be reacted is reacted.
- the vinylidenes are advantageous in that they are more stable at higher temperatures than the alkylidenes.
- the protected NHC e.g., a saturated Imes ligand as described in U.S. Provisional Patent Application Nos. 60/288,680 and 60/278,311, the contents of each of which are inco ⁇ orated herein by reference
- the time to reach the peak is significantly reduced.
- a high peak exotherm means more catalyst is available for polymerization, indicating that the extractibles are close to zero. Accordingly, the inventive catalysts have better conversion, better properties, even in the presence of fillers and additives.
- Pentane, toluene, benzene, and benzene-c? 6 were dried by passage through solvent purification columns. Pyridine was dried by vacuum transfer from CaH 2 . All phosphines as well as KTp were obtained from commercial sources and used as received. Ruthenium complexes 1-4 and 44-48 were prepared according to literature procedures.
- Synthesis Complex 1 (2.0 grams) was dissolved in toluene (10 mL), and 2- pyridinecarboxaldehyde (1.01 grams, 4 mol equivalents) was added. The reaction flask was purged with argon and the reaction mixture was stirred for approximately 12 hours at about 20 °C to about 25 °C during which time a color change from dark pu ⁇ le to dark blue was observed. The reaction mixture was transferred into 75 mL of cold (about 0 °C) pentane, and a dark blue solid precipitated.
- T max Time to reach maximum temperature
- T max 200.9 °C.
- Glass transition temperature measured by thermal mechanical analysis (TMA) 145 °C.
- Percent residual monomer (toluene extraction at room temperature) 4.57 %.
- KTp (87 mg, 0.34 mmol) and complex 31 (125 mg, 0.17 mmol) were combined in CH 2 CI 2 (10 mL) and stirred for 1 hour.
- Pentane (20 mL) was added to precipitate the salts, and the reaction was stirred for an additional 30 min and then cannula filtered.
- the resulting bright green solution was concentrated, and the solid residue was washed with pentane (2 x 10 mL) and methanol (2 x 10 mL) and dried under vacuum to afford 43 (84 mg, 66% yield) as an analytically pure green powder.
- Crystal, intensity collection, and refinement details were summarized in Table 1.
- the selected crystal was mounted on a glass fiber with Paratone-N oil and transferred to a Bruker SMART 1000 CCD area detector equipped with a Crystal Logic CL24 low- temperature device. Data were collected with ⁇ -scans at seven ⁇ values and subsequently processed with SAINT. No abso ⁇ tion or decay corrections were applied.
- SHELXTL was used to solve (by direct methods and subsequent difference Fourier maps) and to refine (full-matrix least-squares on F 2 ) the structure. There are two molecules in the asymmetric unit.
- T max Time to reach maximum temperature
- T max 246.2 °C.
- Glass transition temperature measured by thermal mechanical analysis (TMA) 175.35 °C.
- TMA thermal mechanical analysis
- Example (2) A 75 g mass of hexylnorbornene was polymerized using
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Abstract
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Priority Applications (5)
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EP02791535.4A EP1423195B1 (en) | 2001-08-01 | 2002-06-14 | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
CA2455893A CA2455893C (en) | 2001-08-01 | 2002-06-14 | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
JP2003516680A JP2005508883A (en) | 2001-08-01 | 2002-06-14 | Hexacoordinate ruthenium or osmium metal carbene metathesis catalyst |
MXPA04001004A MXPA04001004A (en) | 2001-08-01 | 2002-06-14 | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts. |
HK05104174A HK1071323A1 (en) | 2001-08-01 | 2005-05-18 | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
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US30980601P | 2001-08-01 | 2001-08-01 | |
US60/309,806 | 2001-08-01 | ||
US31497801P | 2001-08-24 | 2001-08-24 | |
US60/314,978 | 2001-08-24 | ||
US09/948,115 | 2001-09-05 | ||
US09/948,115 US6610626B2 (en) | 2000-09-05 | 2001-09-05 | Highly active metathesis catalysts generated in situ from inexpensive and air stable precursors |
US10/017,489 US6759537B2 (en) | 2001-03-23 | 2001-12-14 | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
US10/017,489 | 2001-12-14 | ||
US10/138,188 | 2002-03-05 | ||
US10/107,531 | 2002-03-25 | ||
US10/107,531 US6838489B2 (en) | 2001-03-23 | 2002-03-25 | High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor |
US10/138,188 US20030083445A1 (en) | 2001-03-23 | 2002-05-03 | High activity metal carbene metathesis catalysts generated using a thermally activated N-heterocyclic carbene precursor |
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Also Published As
Publication number | Publication date |
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MXPA04001004A (en) | 2004-06-25 |
CN1265882C (en) | 2006-07-26 |
CA2455893A1 (en) | 2003-02-13 |
EP1423195B1 (en) | 2016-03-02 |
CN1561261A (en) | 2005-01-05 |
EP1423195A4 (en) | 2005-06-29 |
HK1071323A1 (en) | 2005-07-15 |
EP1423195A1 (en) | 2004-06-02 |
JP2005508883A (en) | 2005-04-07 |
CA2455893C (en) | 2011-01-18 |
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