US20050261451A1 - Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand - Google Patents
Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand Download PDFInfo
- Publication number
- US20050261451A1 US20050261451A1 US11/094,102 US9410205A US2005261451A1 US 20050261451 A1 US20050261451 A1 US 20050261451A1 US 9410205 A US9410205 A US 9410205A US 2005261451 A1 US2005261451 A1 US 2005261451A1
- Authority
- US
- United States
- Prior art keywords
- substituted
- hydrocarbyl
- heteroatom
- hydrocarbylene
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003446 ligand Substances 0.000 title claims abstract description 75
- 238000005865 alkene metathesis reaction Methods 0.000 title claims abstract description 30
- 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 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 title abstract description 153
- 230000000694 effects Effects 0.000 title description 29
- 238000006798 ring closing metathesis reaction Methods 0.000 claims abstract description 24
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims abstract description 21
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 claims description 97
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims description 52
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 51
- 125000003118 aryl group Chemical group 0.000 claims description 50
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 20
- 125000000524 functional group Chemical group 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 18
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 125000004429 atom Chemical group 0.000 claims description 13
- 230000007935 neutral effect Effects 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 11
- 125000000623 heterocyclic group Chemical group 0.000 claims description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- -1 acyclic olefins Chemical class 0.000 abstract description 50
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 14
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 46
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 41
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 38
- 229910052707 ruthenium Inorganic materials 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 35
- 239000007787 solid Substances 0.000 description 34
- 125000000217 alkyl group Chemical group 0.000 description 30
- 125000004432 carbon atom Chemical group C* 0.000 description 29
- 125000001424 substituent group Chemical group 0.000 description 27
- 125000003342 alkenyl group Chemical group 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 125000000304 alkynyl group Chemical group 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 15
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 14
- LYUUVYQGUMRKOV-UHFFFAOYSA-N Diethyl diallylmalonate Chemical compound CCOC(=O)C(CC=C)(CC=C)C(=O)OCC LYUUVYQGUMRKOV-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000005649 metathesis reaction Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 0 C[C@](**N(*[C@](C*)CCCC*)O)*N*C1=C(*SSO)C1 Chemical compound C[C@](**N(*[C@](C*)CCCC*)O)*N*C1=C(*SSO)C1 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000003039 volatile agent Substances 0.000 description 11
- 150000004820 halides Chemical class 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 7
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 7
- UJHRXZWERCGWQW-UHFFFAOYSA-N 2-but-3-enylpyridine Chemical compound C=CCCC1=CC=CC=N1 UJHRXZWERCGWQW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 125000002877 alkyl aryl group Chemical group 0.000 description 6
- 229910052786 argon Inorganic materials 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
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052762 osmium Inorganic materials 0.000 description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 241000894007 species Species 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 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 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 238000005686 cross metathesis reaction Methods 0.000 description 4
- GDWAYKGILJJNBB-UHFFFAOYSA-N diethyl 2-prop-2-enylpropanedioate Chemical compound CCOC(=O)C(CC=C)C(=O)OCC GDWAYKGILJJNBB-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 125000003367 polycyclic group Chemical group 0.000 description 4
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 3
- LSMWOQFDLBIYPM-UHFFFAOYSA-N 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-2h-imidazol-1-ium-2-ide Chemical compound CC1=CC(C)=CC(C)=C1N1[C-]=[N+](C=2C(=CC(C)=CC=2C)C)CC1 LSMWOQFDLBIYPM-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-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
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical compound O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 238000010535 acyclic diene metathesis reaction Methods 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000005133 alkynyloxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000005621 boronate group Chemical group 0.000 description 2
- 125000001626 borono group Chemical group [H]OB([*])O[H] 0.000 description 2
- 125000000707 boryl group Chemical group B* 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
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- IQZZFVDIZRWADY-UHFFFAOYSA-N isocoumarin Chemical compound C1=CC=C2C(=O)OC=CC2=C1 IQZZFVDIZRWADY-UHFFFAOYSA-N 0.000 description 2
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 description 2
- 125000000394 phosphonato group Chemical group [O-]P([O-])(*)=O 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- 125000004739 (C1-C6) alkylsulfonyl group Chemical group 0.000 description 1
- 125000006710 (C2-C12) alkenyl group Chemical group 0.000 description 1
- 125000006711 (C2-C12) alkynyl group Chemical group 0.000 description 1
- JZTKNVMVUVSGJF-UHFFFAOYSA-N 1,2,3,5-oxatriazole Chemical compound C=1N=NON=1 JZTKNVMVUVSGJF-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BBVIDBNAYOIXOE-UHFFFAOYSA-N 1,2,4-oxadiazole Chemical compound C=1N=CON=1 BBVIDBNAYOIXOE-UHFFFAOYSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- WTPCCFHCHCMJIT-UHFFFAOYSA-N 1,2,5-oxathiazine Chemical compound O1SC=CN=C1 WTPCCFHCHCMJIT-UHFFFAOYSA-N 0.000 description 1
- VCZQYTJRWNRPHF-UHFFFAOYSA-N 1,2-dioxin Chemical compound O1OC=CC=C1 VCZQYTJRWNRPHF-UHFFFAOYSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- OHOXMCCFSFSRMD-UHFFFAOYSA-N 1,3-oxathiole Chemical compound C1OC=CS1 OHOXMCCFSFSRMD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- QWENRTYMTSOGBR-UHFFFAOYSA-N 1H-1,2,3-Triazole Chemical compound C=1C=NNN=1 QWENRTYMTSOGBR-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- LFHLEABTNIQIQO-UHFFFAOYSA-N 1H-isoindole Chemical compound C1=CC=C2CN=CC2=C1 LFHLEABTNIQIQO-UHFFFAOYSA-N 0.000 description 1
- FZKCAHQKNJXICB-UHFFFAOYSA-N 2,1-benzoxazole Chemical compound C1=CC=CC2=CON=C21 FZKCAHQKNJXICB-UHFFFAOYSA-N 0.000 description 1
- VWSZWVLPNPRXTP-UHFFFAOYSA-N 2,2-dimethyl-n-phenylpent-4-en-1-imine Chemical compound C=CCC(C)(C)C=NC1=CC=CC=C1 VWSZWVLPNPRXTP-UHFFFAOYSA-N 0.000 description 1
- ZMBFSJVNWOSYHA-UHFFFAOYSA-N 2,2-dimethyl-n-propan-2-ylpent-4-en-1-imine Chemical compound CC(C)N=CC(C)(C)CC=C ZMBFSJVNWOSYHA-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- ZIVYADMFPMNVMV-UHFFFAOYSA-N 2-but-3-enyl-4-methylpyridine Chemical compound CC1=CC=NC(CCC=C)=C1 ZIVYADMFPMNVMV-UHFFFAOYSA-N 0.000 description 1
- NAJPTAHUWZKKER-UHFFFAOYSA-N 2-but-3-enyl-6-methylpyridine Chemical compound CC1=CC=CC(CCC=C)=N1 NAJPTAHUWZKKER-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-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
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- JZIBVTUXIVIFGC-UHFFFAOYSA-N 2H-pyrrole Chemical compound C1C=CC=N1 JZIBVTUXIVIFGC-UHFFFAOYSA-N 0.000 description 1
- KGWNRZLPXLBMPS-UHFFFAOYSA-N 2h-1,3-oxazine Chemical compound C1OC=CC=N1 KGWNRZLPXLBMPS-UHFFFAOYSA-N 0.000 description 1
- YHWMFDLNZGIJSD-UHFFFAOYSA-N 2h-1,4-oxazine Chemical compound C1OC=CN=C1 YHWMFDLNZGIJSD-UHFFFAOYSA-N 0.000 description 1
- ACVSHQGHCWUJFU-UHFFFAOYSA-N 2h-imidazole Chemical compound C1N=CC=N1 ACVSHQGHCWUJFU-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VXIKDBJPBRMXBP-UHFFFAOYSA-N 3H-pyrrole Chemical compound C1C=CN=C1 VXIKDBJPBRMXBP-UHFFFAOYSA-N 0.000 description 1
- BWCDLEQTELFBAW-UHFFFAOYSA-N 3h-dioxazole Chemical compound N1OOC=C1 BWCDLEQTELFBAW-UHFFFAOYSA-N 0.000 description 1
- RELAJOWOFXGXHI-UHFFFAOYSA-N 3h-oxathiole Chemical compound C1SOC=C1 RELAJOWOFXGXHI-UHFFFAOYSA-N 0.000 description 1
- MSTDXOZUKAQDRL-UHFFFAOYSA-N 4-Chromanone Chemical compound C1=CC=C2C(=O)CCOC2=C1 MSTDXOZUKAQDRL-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- MRUWJENAYHTDQG-UHFFFAOYSA-N 4H-pyran Chemical compound C1C=COC=C1 MRUWJENAYHTDQG-UHFFFAOYSA-N 0.000 description 1
- UCZQXJKDCHCTAI-UHFFFAOYSA-N 4h-1,3-dioxine Chemical compound C1OCC=CO1 UCZQXJKDCHCTAI-UHFFFAOYSA-N 0.000 description 1
- BMRPOOWUTVUBRI-UHFFFAOYSA-N 4h-oxazine Chemical compound C1C=CON=C1 BMRPOOWUTVUBRI-UHFFFAOYSA-N 0.000 description 1
- CLRIMWMVEVYXAK-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene Chemical compound CCC1C=CC=C1 CLRIMWMVEVYXAK-UHFFFAOYSA-N 0.000 description 1
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- PDBSZKLTFPMQGI-GBKNIRSUSA-N C/C=C\C.CC1=C(C)C=C2C=CC=CC2=C1.CC1=C(C)C=CC=C1.CC1=CC=CC2=CC=CC(C)=C12.CC1CCCCC1C.CCC.CCCC Chemical compound C/C=C\C.CC1=C(C)C=C2C=CC=CC2=C1.CC1=C(C)C=CC=C1.CC1=CC=CC2=CC=CC(C)=C12.CC1CCCCC1C.CCC.CCCC PDBSZKLTFPMQGI-GBKNIRSUSA-N 0.000 description 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 description 1
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 description 1
- CVYUPAJBPLIDDA-UHFFFAOYSA-N C=CC=[Ru] Chemical compound C=CC=[Ru] CVYUPAJBPLIDDA-UHFFFAOYSA-N 0.000 description 1
- RJPCECSVTVQIKX-UHFFFAOYSA-D CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CC3=C(C=CC=C3)[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC3=C(C=CC=C3)[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC[P+]2(C2=CC=CC=C2)C2=CC=CC=C2)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC[N+]2(C)C)C(C)=C1 Chemical compound CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CC3=C(C=CC=C3)[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC3=C(C=CC=C3)[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC[N+]2(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC[P+]2(C2=CC=CC=C2)C2=CC=CC=C2)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC[N+]2(C)C)C(C)=C1 RJPCECSVTVQIKX-UHFFFAOYSA-D 0.000 description 1
- RQALXBYYQLKGRD-UHFFFAOYSA-H CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CC3=C(C=CC=C3)[O+]2C(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru](Cl)(Cl)(=CC2=CC=CC=C2)[PH](C2CCCCC2)(C2CCCCC2)C2CCCCC2)C(C)=C1.[CH2+][Ru-2]([CH2+])(Cl)(Cl)(=CC1=CC=CC=C1)C1N(C2=C(C)C=C(C)C=C2C)CCN1C1=C(C)C=C(C)C=C1C Chemical compound CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CC3=C(C=CC=C3)[O+]2C(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru](Cl)(Cl)(=CC2=CC=CC=C2)[PH](C2CCCCC2)(C2CCCCC2)C2CCCCC2)C(C)=C1.[CH2+][Ru-2]([CH2+])(Cl)(Cl)(=CC1=CC=CC=C1)C1N(C2=C(C)C=C(C)C=C2C)CCN1C1=C(C)C=C(C)C=C1C RQALXBYYQLKGRD-UHFFFAOYSA-H 0.000 description 1
- VLOCVJMOAXPDSU-SGFNUPLXSA-F CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C(C)(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C2CCCCC2)C(C)=C1 Chemical compound CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C(C)(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C(C)C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C2CCCCC2)C(C)=C1 VLOCVJMOAXPDSU-SGFNUPLXSA-F 0.000 description 1
- MICBXNHVRJKMEO-CHTSVRGOSA-D CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C2=CC=CC=C2)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C(C)=CC=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC(C)=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC=C3)C(C)=C1 Chemical compound CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCC(C)(C)C=[N+]2C2=CC=CC=C2)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C(C)=CC=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC(C)=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC=C3)C(C)=C1.CC1=CC(C)=C(N2CCN(C3=C(C)C=C(C)C=C3C)C2[Ru-]2(Cl)(Cl)=CCCC3=[N+]2C=CC=C3)C(C)=C1 MICBXNHVRJKMEO-CHTSVRGOSA-D 0.000 description 1
- RIKWDTOAIJISMX-UHFFFAOYSA-N CN[C-]1(C)(C)=CC2=C(C=CC=C2)[O+]1C.C[C-]1(C)(C)=CCCC2=[N+]1C=CC=C2 Chemical compound CN[C-]1(C)(C)=CC2=C(C=CC=C2)[O+]1C.C[C-]1(C)(C)=CCCC2=[N+]1C=CC=C2 RIKWDTOAIJISMX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- CVQUWLDCFXOXEN-UHFFFAOYSA-N Pyran-4-one Chemical compound O=C1C=COC=C1 CVQUWLDCFXOXEN-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910019854 Ru—N Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- GCWOQVGAECOHIK-UHFFFAOYSA-N [Ru]CCC1=CC=CC=N1 Chemical compound [Ru]CCC1=CC=CC=N1 GCWOQVGAECOHIK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000005248 alkyl aryloxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004419 alkynylene group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000004467 aryl imino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 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
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 125000002579 carboxylato group Chemical group [O-]C(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
- 229940052810 complex b Drugs 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- DLKYQYMXPSONJP-UHFFFAOYSA-N cyclopenta[b]pyridine Chemical compound C1=C[N]C2=CC=CC2=C1 DLKYQYMXPSONJP-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 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
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004997 halocarbonyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- JCYWCSGERIELPG-UHFFFAOYSA-N imes Chemical compound CC1=CC(C)=CC(C)=C1N1C=CN(C=2C(=CC(C)=CC=2C)C)[C]1 JCYWCSGERIELPG-UHFFFAOYSA-N 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 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
- MKHHKAFWMAYADE-UHFFFAOYSA-N isochromen-3-one Chemical compound C1=CC=CC2=COC(=O)C=C21 MKHHKAFWMAYADE-UHFFFAOYSA-N 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RIFHJAODNHLCBH-UHFFFAOYSA-N methanethione Chemical group S=[CH] RIFHJAODNHLCBH-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MEYIFNOHQMJVSK-UHFFFAOYSA-N n,2,2-trimethylpent-4-en-1-imine Chemical compound CN=CC(C)(C)CC=C MEYIFNOHQMJVSK-UHFFFAOYSA-N 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
- 125000004370 n-butenyl group Chemical group [H]\C([H])=C(/[H])C([H])([H])C([H])([H])* 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
- IYVQMNNHQGDUDH-UHFFFAOYSA-N n-cyclohexyl-2,2-dimethylpent-4-en-1-imine Chemical compound C=CCC(C)(C)C=NC1CCCCC1 IYVQMNNHQGDUDH-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NBIHPISJSSXWAS-UHFFFAOYSA-N n-tert-butyl-2,2-dimethylpent-4-en-1-imine Chemical compound CC(C)(C)N=CC(C)(C)CC=C NBIHPISJSSXWAS-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 150000002907 osmium Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical compound C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 description 1
- ATYBXHSAIOKLMG-UHFFFAOYSA-N oxepin Chemical compound O1C=CC=CC=C1 ATYBXHSAIOKLMG-UHFFFAOYSA-N 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- XLFDEQZWKMCBSH-UHFFFAOYSA-N pent-4-enyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC=C)C1=CC=CC=C1 XLFDEQZWKMCBSH-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- FLTFWLUOHKERMJ-UHFFFAOYSA-N pyrano[3,4-b]pyrrole Chemical compound C1=COC=C2N=CC=C21 FLTFWLUOHKERMJ-UHFFFAOYSA-N 0.000 description 1
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical compound C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
- C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
- C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
Definitions
- This invention relates generally to olefin metathesis catalysts, and more particularly pertains to new Group 8 transition metal complexes that are useful as latent olefin metathesis catalysts.
- the invention has utility in the fields of catalysis, organic synthesis, and organometallic chemistry.
- Olefin metathesis catalysis is a powerful technology, which in recent years has received tremendous attention as a versatile method for the formation of carbon-carbon bonds and has numerous applications in organic synthesis and polymer chemistry (R. H. Grubbs, Handbook of Metathesis , Vol. 2 and 3; Wiley V C H, Weinheim, 2003).
- the family of olefin metathesis reactions includes ring-closing metathesis (RCM), cross metathesis (CM), ring-opening metathesis polymerization (ROMP), and acyclic diene metathesis polymerization (ADMET).
- L represents an NHC ligand such as 1,3-dimesitylimidazole-2-ylidene (IMes) and 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene (sIMes)
- X represents a halogen (e.g., Cl, Br, or I)
- R represents an alkyl, cycloalkyl, or aryl group (e.g., butyl, cyclohexyl, or phenyl)
- R′ represents an alkyl, alkenyl, or aryl group (e.g., methyl
- L represents an imidazolylidine ligand
- L′ represents a pyridine (Py) or substituted pyridine ligand
- X represents a halogen (e.g., Cl, Br, or I
- a different strategy to tune olefin metathesis catalysts involves linking two of the ligands that are attached to the metal center.
- chelating carbene species reported by Hoveyda and others (Gaber et al. (2000) J. Am. Chem. Soc. 122, 8168-8179; Kingsbury et al. (1999) J. Am. Chem. Soc. 121, 791-799; Harrity et al. (1997) J. Am. Chem. Soc. 119, 1488-1489; Harrity et al. (1998) J. Am. Chem. Soc. 120, 2343-2351). These catalysts are exceptionally stable and can be purified by column chromatography in air.
- Catalyst PR-1 and PR-2 Representative such catalysts, designated Catalyst PR-1 and PR-2, are illustrated in FIG. 1 .
- Catalyst PR-2 combines excellent stability and enhanced activity, and actively promotes the cross-metathesis of acrylonitrile and terminal olefins in moderate to excellent yields.
- a latent olefin metathesis catalyst that contains a chelating carbene ligand is the 2-pyridylethanyl ruthenium carbene complex (PR 3 )(Cl) 2 Ru(CH(CH 2 ) 2 —C,N-2-C 5 H 4 N) by reacting a (PR 3 ) 2 (Cl) 2 Ru ⁇ CHR′ complex with 2-(3-butenyl)pyridine developed by van der Schaaf (van der Schaaf et al. (2000) J. Organometallic Chemistry 606, 65-74).
- These types of catalysts are also described in U.S. Pat. No. 6,306,987.
- the present invention relates to novel high-activity but latent olefin metathesis catalysts that comprise an NHC ligand and a chelating carbene ligand.
- catalysts are provided that have a latency period on the order of minutes to hours, or even longer. It has also been surprisingly discovered that the initiation rate of some of these catalysts can be substantially varied via simple isomerization of the complexes and that the reactivity can be tuned over a wide range by controlling the ratio of the different isomers.
- the catalysts are particularly useful in the RCM of acyclic olefins and the ROMP of cyclic olefins.
- the present catalytic complexes generally have the structure of formula (I)
- a method for carrying out an olefin metathesis reaction is provided using the aforementioned complexes as reaction catalysts.
- FIG. 1 provides the molecular structures of two metathesis catalysts of the prior art, indicated as Pr-1 and Pr-2.
- FIG. 2 provides the molecular structures of two representative catalytic complexes of the invention, indicated as Catalysts 2 a and 2 b.
- FIG. 3 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2 a.
- FIG. 4 depicts an ORTEP drawing of the X-ray crystal structure of Catalyst 2 b.
- FIG. 5 provides the molecular structures of two representative catalytic complexes of the invention, indicated as Catalysts 4 and 5 .
- FIG. 6 provides the molecular structures of additional representative catalytic complexes of the invention.
- FIG. 7 schematically depicts a method for synthesizing representative catalytic complexes 2 a , 4 and 5 of the invention.
- FIG. 8 schematically depicts a method for synthesizing representative catalytic complexes 2 b of the invention.
- FIG. 9 provides the molecular structure of additional representative catalytic complexes of the invention.
- FIG. 10 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 1 , 2 a , 2 b and 12 , as described in Example 15.
- FIG. 11 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 2 a , 4 and 5 , as described in Example 16.
- FIG. 12 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 2 a , 7 and 8 , as described in Example 17.
- FIG. 13 illustrates the percent of reactant converted versus time for the RCM reaction of diethyldiallyl malonate using catalysts 7 , 8 , 9 , 10 , and 11 , as also described in Example 17.
- FIG. 14 provides the exotherms for the RCM reaction of diethyldiallyl malonate to assess the activity of catalysts 6 and 8 , as described in Example 18.
- FIG. 15 provides the exotherms for the ROMP reaction catalyzed by catalysts 2 a and 2 b , as described in Example 19.
- FIG. 16 provides the exotherms for the ROMP reaction catalyzed by catalysts 2 a , 2 b and 12 , as also described in Example 19.
- FIG. 17 provides the exotherms for the ROMP reactions catalyzed using different mixtures of 2 a and 2 b , as described in Example 20.
- FIG. 18 provides the exotherms for the ROMP reaction catalyzed by catalysts 2 a , 7 and 8 , as described in Example 21.
- alkyl refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 20 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms.
- lower alkyl intends an alkyl group of 1 to 6 carbon atoms
- cycloalkyl intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms.
- substituted alkyl refers to alkyl substituted with one or more substituent groups
- heteroatom-containing alkyl and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.
- alkylene refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.
- alkenyl refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 20 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like.
- Preferred alkenyl groups herein contain 2 to about 12 carbon atoms.
- lower alkenyl intends an alkenyl group of 2 to 6 carbon atoms
- specific term “cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms.
- substituted alkenyl refers to alkenyl substituted with one or more substituent groups
- heteroatom-containing alkenyl and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.
- alkenylene refers to a difunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.
- alkynyl refers to a linear or branched hydrocarbon group of 2 to about 20 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms.
- substituted alkynyl refers to alkynyl substituted with one or more substituent groups
- heteroatom-containing alkynyl and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.
- alkynylene refers to a difunctional alkynyl group, where “alkynyl” is as defined above.
- alkoxy intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as —O-alkyl where alkyl is as defined above.
- a “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms.
- alkenyloxy and lower alkenyloxy respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage
- alkynyloxy and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.
- aryl refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety).
- Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms.
- Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like.
- Substituted aryl refers to an aryl moiety substituted with one or more substituent groups
- heteroatom-containing aryl and “heteroaryl” refer to aryl substituent, in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.
- aryloxy refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above.
- An “aryloxy” group may be represented as —O-aryl where aryl is as defined above.
- Preferred aryloxy groups contain 5 to 20 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms.
- aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.
- alkaryl refers to an aryl group with an alkyl substituent
- aralkyl refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above.
- Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms.
- Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like.
- aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like.
- alkaryloxy and aralkyloxy refer to substituents of the formula —OR wherein R is alkaryl or aralkyl, respectively, as just defined.
- acyl refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl
- acyloxy refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as defined above.
- cyclic refers to alicyclic or aromatic substituents that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic.
- alicyclic is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.
- halo and “halogen” are used in the conventional sense to refer to a chloro, bromo, and fluoro or iodo substituent.
- Hydrocarbyl refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like.
- lower hydrocarbyl intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
- hydrocarbylene intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species.
- lower hydrocarbylene intends a hydrocarbylene group of 1 to 6 carbon atoms.
- Substituted hydrocarbyl refers to hydrocarbyl substituted with one or more substituent groups
- heteroatom-containing hydrocarbyl and heterohydrocarbyl refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom
- substituted hydrocarbylene refers to hydrocarbylene substituted with one or more substituent groups
- heteroatom-containing hydrocarbylene and heterohydrocarbylene refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom.
- hydrocarbyl and hydrocarbylene are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.
- heteroatom-containing hydrocarbyl group refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur.
- heteroalkyl refers to an alkyl substituent that is heteroatom-containing
- heterocyclic refers to a cyclic substituent that is heteroatom-containing
- heteroaryl and heteroaromatic respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like.
- a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.”
- substituted as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents.
- substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C 1 -C 20 alkoxy, C 2 -C 20 alkenyloxy, C 2 -C 20 alkynyloxy, C 5 -C 24 aryloxy, C 6 -C 24 aralkyloxy, C 6 -C 24 alkaryloxy, acyl (including C 2 -C 20 alkylcarbonyl (—CO-alkyl) and C 6 -C 24 arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C 2 -C 20 alkylcarbonyloxy (—O—CO-alkyl) and C 6 -C 24 arylcarbonyloxy (—O—CO-aryl)), C 2 -C 20 alkoxycarbonyl (—(CO)—O-alkyl), C 6 -C 24 aryloxycarbonyl (——C
- the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above.
- the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.
- the invention provides a Group 8 transition metal complex having the structure of formula (I)
- the metal center designated as M is a Group 8 transition metal, preferably ruthenium or osmium. In a particularly preferred embodiment, M is ruthenium.
- R 1 and R 2 are independently selected from hydrogen, hydrocarbyl (e.g., C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, C 6 -C 24 alkaryl, C 6 -C 24 aralkyl,
- R 1 and R 2 are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R 1 and R 2 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like.
- R 1 and R 2 are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C 1 -C 20 alkyl, substituted C 1 -C 20 alkyl, C 1 -C 20 heteroalkyl, substituted C 1 -C 20 heteroalkyl, C 5 -C 24 aryl, substituted C 5 -C 24 aryl, C 5 -C 24 heteroaryl, C 6 -C 24 aralkyl, C 6 -C 24 alkaryl, and halide.
- any substituents present are hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 14 aryl, substituted C 5 -C 14 aryl, or halide. More preferably, R 1 and R 2 are mesityl.
- R 1 and R 2 are independently selected from hydrogen, C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 substituted aryl, C 1 -C 20 functionalized alkyl, C 2 -C 20 functionalized alkenyl, C 2 -C 20 functionalized alkynyl, or C 5 -C 24 functionalized substituted aryl where the functional group(s) (“Fn”) may independently be one or more or the following:
- Q is typically selected from hydrocarbylene (e.g., C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), substituted hydrocarbylene (e.g., substituted C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), heteroatom-containing hydrocarbylene (e.g., C 1 -C 20 heteroalkylene, C 2 -C 20 heteroalkenylene, C 2 -C 20 heteroalkynylene, C 5 -C 24 heteroarylene, heteroatom-containing C 6 -C 24 aralkylene, or heteroatom-containing C 6 -C 24 alkarylene
- Q is a two-atom linkage having the structure —CR 3 R 4 —CR 5 R 6 — or —CR ⁇ CR 5 —, preferably —R 3 R 4 —CR 5 R 6 —, wherein R 3 , R 4 , R 5 , and R 6 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups.
- Examples of functional groups here include carboxyl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 5 -C 24 alkoxycarbonyl, C 2 -C 24 acyloxy, C 1 -C 20 alkylthio, C 5 -C 24 arylthio, C 1 -C 20 alkylsulfonyl, and C 1 -C 20 alkylsulfinyl, optionally substituted with one or more moieties selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 14 aryl, hydroxyl, sulfhydryl, formyl, and halide.
- R 3 , R 4 , R 5 , and R 6 are preferably independently selected from hydrogen, C 1 -C 12 alkyl, substituted C 1 -C 12 alkyl, C 1 -C 12 heteroalkyl, substituted C 1 -C 12 heteroalkyl, phenyl, and substituted phenyl.
- any two of R 3 , R 4 , R 5 , and R 6 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C 4 -C 12 alicyclic group or a C 5 or C 6 aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.
- a substituted or unsubstituted, saturated or unsaturated ring structure e.g., a C 4 -C 12 alicyclic group or a C 5 or C 6 aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.
- X 1 and X 2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring.
- X 1 and X 2 are each independently hydrogen, halide, or one of the following groups: C 1 -C 20 alkyl, C 5 -C 24 aryl, C 1 -C 20 alkoxy, C 5 -C 24 aryloxy, C 2 -C 20 alkoxycarbonyl, C 6 -C 24 aryloxycarbonyl, C 2 -C 24 acyl, C 2 -C 24 acyloxy, C 1 -C 20 alkylsulfonato, C 5 -C 24 arylsulfonato, C 1 -C 20 alkylsulfanyl, C 5 -C 24 arylsulfanyl, C 1 -C 20 alkylsulfinyl, C 5 -C 24
- X 1 and X 2 may be substituted with one or more moieties, if the X 1 and/or X 2 substituent permits, wherein the substituents are typically although not necessarily selected from C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 5 -C 24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, and phenyl.
- X 1 and X 2 are halide, benzoate, C 2 -C 6 acyl, C 2 -C 6 alkoxycarbonyl, C 1 -C 6 alkyl, phenoxy, C 1 -C 6 alkoxy, C 1 -C 6 alkylsulfanyl, aryl, or C 1 -C 6 alkylsulfonyl.
- X 1 and X 2 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 1 and X 2 are each chloride.
- L 1 is a neutral electron donor ligand which is coordinated to the metal center.
- L 1 may be heterocyclic, in which case it is generally selected from:
- L 1 may also be an amine, an imine, a phosphine, an ether, or a thioether.
- L 1 is selected from pyridines, amines, phosphines, imines, ethers, thioethers, furans, and pyrans.
- L 2 is selected from NR 7 R 8 , PR 7 R 8 , N ⁇ CR 7 R 8 , and R 7 C ⁇ NR 8 , where R 7 and R 8 are independently selected from substituted and/or heteroatom-containing C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 5 -C 24 aryl, or R 7 and R 8 taken together can form a cyclic group, e.g., piperidyl (including substituted piperidyl). Any functional groups present on L 1 , L 2 , R 7 , or R 8 will generally be selected from the Fn groups set forth above.
- Examples of preferred such catalysts are those wherein L 2 is NR 7 R 8 , having the structure of formula (II) wherein Q, R 1 , R 2 , R 7 , R 8 , X 1 , X 2 , L 1 , Y, Z, ⁇ , and p are as defined above.
- Preferred R 7 and R 8 substituents in this embodiment are C 1 -C 12 alkyl or C 5 -C 12 aryl, e.g., methyl, isopropyl, t-butyl, cyclohexyl, and phenyl, and preferred Y groups are —CH 2 —, —CH 2 CH 2 — and substituted analogs thereof.
- L 2 and Z can be linked through an unsaturated bond, i.e., the dashed line indicating a bond at a may also represent a double bond or a bond linking adjacent atoms in an aromatic ring.
- L 2 is selected from NR 7 and PR 7 , and preferably is NR 7 where R 7 is as defined previously.
- the complex may be contain an imine ligand (i.e., containing the moiety —Z ⁇ NR 7 ), or may contain a pyridine ring in which N and Z are adjacent atoms in a pyridyl group. Examples of preferred such catalysts in which the complex contains a pyridine ring or an imine moiety are encompassed by structural formulae (IV) and (V), respectively:
- R 7 substituents are C 1 -C 12 alkyl or C 5 -C 12 aryl, e.g., methyl, isopropyl, t-butyl, cyclohexyl, and phenyl, and preferred Y groups are substituted or unsubstituted methylene or ethylene linkages.
- catalytic complexes encompassed by formulae (IV) and (V) include, but are not limited to, the following:
- Y and Z are linkages independently selected from hydrocarbylene (e.g., C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), substituted hydrocarbylene (e.g., substituted C 1 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, C 5 -C 24 arylene, C 6 -C 24 alkarylene, or C 6 -C 24 aralkylene), heteroatom-containing hydrocarbylene (e.g., C 1 -C 20 heteroalkylene, C 2 -C 20 heteroalkenylene, C 2 -C 20 heteroalkynylene, C 5 -C 24 heteroarylene, heteroatom-containing C 6 -C 24 aralkylene, or heteroatom-containing C 6 -C
- Organic diradicals that can serve as Y and/or Z include, by way of example, the following groups: methylene (VI), ethylene (VII), vinylene (VIII), phenylene (IX), cyclohexylene (X), and naphthylenes (XI) and (XII). These organic diradicals may also serve as the linkage Q.
- M is ruthenium
- Q is ethylene (II)
- X 1 and X 2 are chloride
- p is zero.
- R 1 and R 2 are mesityl (2,4,6-trimethylphenyl).
- n is zero.
- Exemplary catalysts of the invention are 2 a and 2 b , the molecular structures of which are provided above and in FIG. 2 , wherein M is ruthenium, L 2 is substituted or unsubstituted pyridyl, R 1 and R 2 are mesityl (2,4,6-trimethylphenyl), Q is ethylene (II), X 1 and X 2 are chloride, Y is ethylene (II), m is 1, and n and p are zero.
- These new catalysts can be prepared by reacting RuCl 2 (sIMes)(PCy 3 )(CHPh) (Catalyst 1 ) and 2-(3-butenyl)pyridine in dichloromethane at 40° C. (see Example 1).
- catalyst 2 a can be obtained either in pure form or as a mixture of isomers 2 a and 2 b .
- This finding was quite surprising, because the known ruthenium carbene olefin metathesis catalysts typically have a configuration like that of 2 a , namely a C S symmetric square pyramidal geometry where the apical position is occupied by the carbene ligand, and the equatorial positions by two trans anionic ligands and two trans neutral electron donating ligands.
- the complex is of C 1 symmetry and contains two equatorial cis anionic ligands and two equatorial cis neutral electron donating ligands.
- Catalyst 2 a can also be prepared by reaction of (sIMes)(py) 2 (Cl) 2 Ru ⁇ CHPh (complex 3 ) with 1.5 equivalent of 2-(3-butenyl)-pyridine in dichloromethane at room temperature for 30 minutes (Example 2).
- this method is amenable to the synthesis of complexes (sIMes)(Cl) 2 Ru(CH(CH 2 ) 2 —C,N-2-(4-Me)-C 5 H 3 N) and Ru(CH(CH 2 ) 2 —C,N-2-(6-Me)-C 5 H 3 N), also shown in FIG. 7 .
- the catalysts of the invention may be synthesized and used in catalyzing olefin metathesis reactions using the procedures described in the examples herein or variations thereof which will be apparent to one of skill in the art.
- Another embodiment of the present invention is a method for the use of the present catalysts, including 2 a and 2 b , for the metathesis of olefins.
- both isomers exhibit large differences in olefin metathesis activity (e.g., in RCM and ROMP). These activity differences enable tuning of the catalyst by simple isomerization of the complex in lieu of the strategies of the prior art, such as utilization of additives or complicated and time-consuming catalyst design involving ligand exchanges.
- the catalysts may be attached to a solid support; as understood in the field of catalysis, suitable solid supports may be of synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic.
- Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect, if indirect, typically between a functional group on a support surface and a ligand or substituent on the catalytic complex.
- the reactions are carried out under conditions normally used in olefin metathesis reactions catalyzed by the Grubbs family of metathesis catalysts. See, e.g., U.S. Pat. Nos. 5,312,940, 5,342,909, 5,831,108, 5,969,170, 6,111,121, and 6,211,391 to Grubbs et al.
- a 0.1 M solution of catalyst 2 a in CD 2 Cl 2 was prepared and transferred to an NMR tube, which was capped and taken out of the glove box.
- the NMR tube was left in an oil bath at 40° C. and the reaction was monitored by 1 H NMR spectroscopy.
- the ratio of 2 b to 2 a in the mixture was 30/70 after 24 hours; 60/40 after 48 hours; 70/30 after 72 hours; and 78/22 after 96 hours.
- the 1 H NMR spectra for catalysts 2 a , 4 and 5 are consistent with complexes of C s symmetry, where the resonances for each of the para methyl groups of the mesityl rings, the ortho methyl groups of the same rings and the ethylene bridge of the sIMes ligand appear as singlets [the 1 H NMR singlets described are consistent with a C s symmetry and free rotation of the sIMes ligand around the Ru—C bond (on the NMR time-scale)].
- Catalyst 2 b appears as a ruthenium carbene of C 1 symmetry, displaying six nonequivalent methyl groups on the mesityl rings, four nonequivalent protons on the ethylene bridge of the sIMes ligand and 4 nonequivalent protons on the ethylene bridge of the pyridyl ligand in the 1 H NMR spectrum.
- Pure isolated 2 a dissolved in CD 2 Cl 2 (0.1 M), is slowly converted to a 22:78 mixture of 2 a : 2 b at 40° C. over the course of 96 hours and pure isolated 2 b forms a similar mixture under the same conditions.
- This type of ligand arrangement is relatively rare for ruthenium carbene complexes, although it has been observed in a few cases [ruthenium complexes containing chelating bisphosphine ligands and cis chlorides have been described: see, e.g., Hansen et al. (1999) Angew. Chem., Int. Ed. 38, 1273-1276; Hansen et al. (1999) Chem.
- the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of the different catalysts.
- 1 mol % of catalyst was added to a 0.1 M solution of diethyldiallyl malonate in dichloromethane and the reaction was allowed to proceed at 25° C. and was monitored by gas-chromatography ( FIG. 10 ).
- 2 a is much slower than 1 ( ⁇ 20% conversion after 100 min versus ⁇ 100% conversion, respectively, under the conditions used)
- 2 b is much slower than 2 a ( ⁇ 2% conversion after 100 min under the conditions used)
- 12 is much slower than 2 b.
- the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 2 a , 4 and 5 .
- 2.5 mol % of catalyst (0.0052 mmol) was dissolved in C 6 D 6 (0.65 mL) in an NMR tube fitted with a teflon septum screw-cap. The resulting solution was allowed to equilibrate in the NMR probe at 40° C.
- Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M was injected into the NMR tube neat and the reaction was monitored by 1 H NMR spectroscopy ( FIG. 11 ).
- Example 16 the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 2 a , 7 and 8 .
- 2.5 mol % of catalyst (0.0052 mmol) was dissolved in C 6 D 6 (0.65 mL) in an NMR tube fitted with a teflon septum screw-cap. The resulting solution was allowed to equilibrate in the NMR probe at 40° C.
- Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M was injected into the NMR tube neat and the reaction was monitored by 1 H NMR spectroscopy ( FIG. 12 ).
- catalyst 7 is faster than 2 a in RCM, while 8 is slower than 2 a.
- Example 16 the ring-closing metathesis of diethyldiallyl malonate was used as a test reaction to compare the activity of catalysts 6 and 8 .
- 2.5 mol % of catalyst (0.0052 mmol) was dissolved in C 6 D 6 (0.65 mL) in an NMR tube fitted with a teflon septum screw-cap. The resulting solution was allowed to equilibrate in the NMR probe at 60° C.
- Diethyldiallyl malonate 50 ⁇ L, 0.207 mmol, 0.30 M
- the reaction was monitored by 1 H NMR spectroscopy ( FIG. 14 ).
- the olefinic resonances integrals of the product relative to that of the starting material were measured with the residual protio solvent peak used as an internal standard.
- the polymerization exotherms for the polymerization catalyzed by catalysts 2 a and 2 b were measured and are shown in FIG. 15 .
- 2 b also initiates the ROMP of DCPD more slowly than 2 a .
- a ROMP of DCPD using 2 a reaches its exotherm within 3 minutes, while the same polymerization catalyzed by 2 b requires more than 25 minutes.
- the difference in reactivity between 2 a and 2 b may be due to the fact that the pyridine ligand in 2 a is trans to the strongly ⁇ -donating NHC ligand and therefore dissociates to give the active 14-electron species much faster than in 2 b .
- the difference in activity between 2 a and 2 b may be purely due to a disparity in initiation rates and does not give any clues regarding the conformation of the metallocyclobutane metathesis intermediates.
- the polymerization exotherms for the polymerization catalyzed by mixtures of catalysts 2 a and 2 b at various ratios of the catalysts were measured and are shown in FIG. 17 .
- the slow isomerization process and large activity difference between catalysts 2 a and 2 b allows for this catalytic system to be tuned by partially isomerizing 2 a to a 2 a : 2 b mixture with the desired initiation rate.
- the use of varying 2 a : 2 b mixtures for the ROMP of DCPD allowed for the control of the times to exotherm as shown in FIG. 17 .
- the polymerization exotherms for the polymerization catalyzed by catalysts 2 a , Ru(Ph-IM) and Ru(Cy-Im) were measured and are shown in FIG. 18 .
- catalyst 7 is faster than 2 a , while 8 is slower than 2 a .
- the same trend was observed in the ROMP of DCPD.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/094,102 US20050261451A1 (en) | 2004-03-29 | 2005-03-29 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
US13/779,190 US8871879B2 (en) | 2004-03-29 | 2013-02-27 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
US14/497,387 US9238709B2 (en) | 2004-03-29 | 2014-09-26 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US55774204P | 2004-03-29 | 2004-03-29 | |
US60415804P | 2004-08-23 | 2004-08-23 | |
US11/094,102 US20050261451A1 (en) | 2004-03-29 | 2005-03-29 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/779,190 Continuation US8871879B2 (en) | 2004-03-29 | 2013-02-27 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
Publications (1)
Publication Number | Publication Date |
---|---|
US20050261451A1 true US20050261451A1 (en) | 2005-11-24 |
Family
ID=35064307
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/094,102 Abandoned US20050261451A1 (en) | 2004-03-29 | 2005-03-29 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
US13/779,190 Active US8871879B2 (en) | 2004-03-29 | 2013-02-27 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
US14/497,387 Active US9238709B2 (en) | 2004-03-29 | 2014-09-26 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/779,190 Active US8871879B2 (en) | 2004-03-29 | 2013-02-27 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
US14/497,387 Active US9238709B2 (en) | 2004-03-29 | 2014-09-26 | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand |
Country Status (8)
Country | Link |
---|---|
US (3) | US20050261451A1 (fr) |
EP (1) | EP1735352B1 (fr) |
JP (2) | JP2007530706A (fr) |
AU (1) | AU2005228434A1 (fr) |
BR (1) | BRPI0509322A (fr) |
MX (1) | MXPA06011302A (fr) |
PL (1) | PL1735352T3 (fr) |
WO (1) | WO2005094345A2 (fr) |
Cited By (36)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100607030B1 (ko) | 2004-03-26 | 2006-08-01 | 롬 앤드 하스 캄파니 | 올레핀 중합 촉매 및 중합 공정 |
US20070270621A1 (en) * | 2003-01-13 | 2007-11-22 | Millis James R | Method for Making Industrial Chemicals |
US20080009598A1 (en) * | 1998-04-06 | 2008-01-10 | Degussa Ag | Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
US20090048459A1 (en) * | 2006-01-10 | 2009-02-19 | Michael John Tupy | Method of making hydrogenated metathesis products |
US20090264672A1 (en) * | 2006-10-13 | 2009-10-22 | Elevance Renewable Sciences, Inc. | Methods of making organic compounds by metathesis |
WO2009142535A1 (fr) | 2008-05-22 | 2009-11-26 | Общество С Ограниченной Ответственностью "Объединённый Центр Исследований И Разработок" | Catalyseur de polymérisation à métathèse de dicyclopentadiène |
US20100145086A1 (en) * | 2006-10-13 | 2010-06-10 | Elevance Renewable Sciences, Inc. | Synthesis of Terminal Alkenes From Internal Alkenes Via Olefin Metathesis |
US20100197920A1 (en) * | 2007-06-20 | 2010-08-05 | Agency For Science, Technology And Research | N-heterocyclic carbene metallacycle catalysts and methods |
US20100282467A1 (en) * | 2009-05-05 | 2010-11-11 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
WO2011005136A1 (fr) | 2009-07-09 | 2011-01-13 | Общество С Ограниченной Ответственностью "Объединённый Центр Исследований И Разработок" | Procédé de production de polydicyclopentadiène et matériaux le contenant |
WO2011043893A2 (fr) * | 2009-10-08 | 2011-04-14 | The Regents Of The University Of California | Catalyseurs moléculaires métal-oxo permettant de générer de l'hydrogène à partir d'eau |
US8067623B2 (en) | 2006-07-12 | 2011-11-29 | Elevance Renewable Sciences, Inc. | Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like |
US8067610B2 (en) | 2006-07-13 | 2011-11-29 | Yann Schrodi | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
WO2011149388A1 (fr) * | 2010-05-27 | 2011-12-01 | Закрытое Акционерное Общество "Сибур Холдинг" | Catalyseur à base de ruthénium de la polymérisation par métathèse de dicylcopentadiène (et variantes) et procédé de production de polycylcopentadiène (et variantes) |
EP2398814A2 (fr) * | 2009-02-18 | 2011-12-28 | Henkel Corporation | Amorceurs à base de ruthénium commutables thermiquement |
WO2013134192A1 (fr) * | 2012-03-05 | 2013-09-12 | California Institute Of Technology | Synthèses de phéromones d'insectes lépidoptères contenant de l'olefine z |
US20140005338A1 (en) * | 2011-03-08 | 2014-01-02 | Zeon Corporation | Polymerizable composition, resin shaped article, and laminate |
EP2742074A1 (fr) * | 2011-08-12 | 2014-06-18 | ExxonMobil Chemical Patents Inc. | Polymères préparés par ouverture de cycle/métathèse croisée |
WO2014134333A1 (fr) | 2013-02-27 | 2014-09-04 | Materia, Inc. | Composition comprenant deux catalyseurs de métathèse d'oléfines de type carbène métallique |
US8846938B2 (en) | 2009-05-07 | 2014-09-30 | Umicore Ag & Co. Kg | Method for preparation of ruthenium-based metathesis catalysts with chelating alkylidene ligands |
US8895771B2 (en) | 2006-10-13 | 2014-11-25 | Elevance Renewable Sciences, Inc. | Methods of making organic compounds by metathesis and hydrocyanation |
WO2015003147A1 (fr) * | 2013-07-03 | 2015-01-08 | Materia, Inc. | Compositions à mouler liquides |
US8993819B2 (en) | 2011-07-12 | 2015-03-31 | Basf Se | Process for preparing cycloheptene |
WO2015076958A1 (fr) * | 2013-11-22 | 2015-05-28 | Exxonmobil Chemical Patents Inc. | Nouveaux polyesters contenant des bras polyoléfiniques |
WO2015115938A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur au ruthénium de polymérisation par métathèse de dicyclopentadiène sous forme de complexe cationique et procédé de production |
WO2015115939A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur de polymérisation par métathèse de dicyclopentadiène et procédé de production |
WO2015115937A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur de polymérisation par métathèse de dicyclopentadiène sous forme de complexe de ruthénium, et procédé de fabrication |
US9181360B2 (en) | 2011-08-12 | 2015-11-10 | Exxonmobil Chemical Patents Inc. | Polymers prepared by ring opening / cross metathesis |
US20160185897A1 (en) * | 2013-02-27 | 2016-06-30 | Materia, Inc. | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
US9382354B2 (en) | 2013-11-22 | 2016-07-05 | Exxonmobil Chemical Patents Inc. | Polyesters containing polyolefin arms |
WO2017053690A1 (fr) * | 2015-09-24 | 2017-03-30 | Materia, Inc. | Catalyseurs de métathèse d'oléfines de type carbène métallique |
WO2017100585A1 (fr) * | 2015-12-10 | 2017-06-15 | Materia, Inc. | Catalyseurs de métathèse d'oléfines |
WO2020201314A1 (fr) | 2019-04-02 | 2020-10-08 | Apeiron Synthesis Spolka Akcyjna | Nouvelle utilisation de complexes métalliques ayant des ligands organiques pour activer des (pré)catalyseurs de ruthénium pour la métathèse d'oléfines |
CN111777647A (zh) * | 2020-07-31 | 2020-10-16 | 山东京博中聚新材料有限公司 | 一种共轭二烯烃聚合物中碳-碳双键的连续氢化生产装置和方法 |
WO2021242636A1 (fr) | 2020-05-29 | 2021-12-02 | Exxonmobil Chemical Patents Inc. | Procédés de production d'oléfines cycliques à partir de polymères et leur re-polymérisation |
CN114106057A (zh) * | 2016-10-19 | 2022-03-01 | 优美科股份公司及两合公司 | Ru亚烷基络合物的合成与表征 |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
PL379879A1 (pl) | 2006-06-07 | 2007-12-10 | Umicore Ag & Co.Kg. | Kompleksy rutenu i osmu, sposób ich wytwarzania oraz ich zastosowanie jako (pre)katalizatorów reakcji metatezy |
KR101461682B1 (ko) * | 2006-06-30 | 2014-11-13 | 에프. 호프만-라 로슈 아게 | 메타세시스 반응용 촉매로서의 신규한 루테늄 착체 |
EP2104566B1 (fr) | 2006-11-21 | 2016-01-27 | California Institute Of Technology | Initiateurs de métathèse d'oléfine portant des ligands thiazol-2-ylidène |
DE102007020694A1 (de) | 2007-05-03 | 2008-11-06 | Evonik Degussa Gmbh | Schwefelhaltige Metathesekatalysatoren |
JP5365625B2 (ja) * | 2008-03-31 | 2013-12-11 | 日本ゼオン株式会社 | 重合性組成物、樹脂成形体、及び架橋樹脂成形体 |
EP2639219B1 (fr) * | 2012-03-14 | 2016-08-10 | Umicore AG & Co. KG | Catalyseurs de métathèse à base de ruthénium et précurseurs pour leur préparation |
AU2016357756B2 (en) | 2015-11-18 | 2021-09-30 | Provivi, Inc. | Production of fatty olefin derivatives via olefin metathesis |
HUE053613T2 (hu) | 2015-11-18 | 2021-07-28 | Provivi Inc | Mikroorganizmusok rovarferomonok és kapcsolódó vegyületek elõállítására |
WO2017214133A2 (fr) | 2016-06-06 | 2017-12-14 | Provivi, Inc. | Production semi-biosynthétique d'alcools gras et d'aldéhydes gras |
MX2019013671A (es) | 2017-05-17 | 2020-01-15 | Provivi Inc | Microorganismos para la produccion de feromonas de insectos y compuestos relacionados. |
US11242363B2 (en) | 2017-12-01 | 2022-02-08 | University Of Florida Research Foundation, Inc. | Compositions and methods for stereoregular ring expansion metathesis polymerization |
CN109794292B (zh) * | 2019-01-10 | 2021-12-07 | 天津大学 | Z-选择性钌卡宾烯烃复分解催化剂及其制备方法与应用 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5312940A (en) * | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
US5969170A (en) * | 1992-04-03 | 1999-10-19 | California Institute Of Technology | High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions |
US6077805A (en) * | 1997-03-06 | 2000-06-20 | Ciba Specialty Chemicals Corporation | Hexacoordinated ruthenium or osmium carbene catalysts |
US6107420A (en) * | 1998-07-31 | 2000-08-22 | California Institute Of Technology | Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes |
US6111121A (en) * | 1995-08-03 | 2000-08-29 | California Institute Of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
US6306987B1 (en) * | 1997-06-27 | 2001-10-23 | Ciba Specialty Chemicals Corporation | Ruthenium and osmium catalysts |
US20020177710A1 (en) * | 2001-03-23 | 2002-11-28 | California Institute Technology; Cymetech, Llc | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
US6803429B2 (en) * | 2001-03-30 | 2004-10-12 | California Institute Of Technology | Selective ring-opening cross-metathesis of cycloolefins |
US6884859B2 (en) * | 2001-08-29 | 2005-04-26 | California Institute Of Technology | Ring-opening metathesis polymerization of bridged bicyclic and polycyclic olefins containing two or more heteroatoms |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1036081B1 (fr) * | 1997-12-04 | 2002-07-17 | Ciba SC Holding AG | Ligand heterocyclyle contenant du ruthenium et des catalyseurs osmium |
DE19815275B4 (de) | 1998-04-06 | 2009-06-25 | Evonik Degussa Gmbh | Alkylidenkomplexe des Rutheniums mit N-heterozyklischen Carbenliganden und deren Verwendung als hochaktive, selektive Katalysatoren für die Olefin-Metathese |
CA2372746C (fr) | 1999-05-24 | 2012-10-02 | California Institute Of Technology | Catalyseurs de metathese de carbene metallique a base d'imidazolidine |
ATE448019T1 (de) * | 2000-08-10 | 2009-11-15 | Trustees Boston College | Wiederverwendbare methathese-katalysatoren |
EP1501784B1 (fr) * | 2002-04-29 | 2019-03-13 | Dow Global Technologies LLC | Procedes chimiques integres a usage industriel pour huiles de graines |
-
2005
- 2005-03-29 US US11/094,102 patent/US20050261451A1/en not_active Abandoned
- 2005-03-29 BR BRPI0509322-8A patent/BRPI0509322A/pt not_active Application Discontinuation
- 2005-03-29 EP EP05743168.6A patent/EP1735352B1/fr active Active
- 2005-03-29 AU AU2005228434A patent/AU2005228434A1/en not_active Abandoned
- 2005-03-29 MX MXPA06011302A patent/MXPA06011302A/es active IP Right Grant
- 2005-03-29 WO PCT/US2005/010548 patent/WO2005094345A2/fr active Application Filing
- 2005-03-29 JP JP2007506479A patent/JP2007530706A/ja not_active Withdrawn
- 2005-03-29 PL PL05743168T patent/PL1735352T3/pl unknown
-
2011
- 2011-12-08 JP JP2011269459A patent/JP5622711B2/ja active Active
-
2013
- 2013-02-27 US US13/779,190 patent/US8871879B2/en active Active
-
2014
- 2014-09-26 US US14/497,387 patent/US9238709B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5312940A (en) * | 1992-04-03 | 1994-05-17 | California Institute Of Technology | Ruthenium and osmium metal carbene complexes for olefin metathesis polymerization |
US5969170A (en) * | 1992-04-03 | 1999-10-19 | California Institute Of Technology | High activity ruthenium and osmium metal carbene complexes for olefin metathesis reactions |
US6111121A (en) * | 1995-08-03 | 2000-08-29 | California Institute Of Technology | High metathesis activity ruthenium and osmium metal carbene complexes |
US6077805A (en) * | 1997-03-06 | 2000-06-20 | Ciba Specialty Chemicals Corporation | Hexacoordinated ruthenium or osmium carbene catalysts |
US6306987B1 (en) * | 1997-06-27 | 2001-10-23 | Ciba Specialty Chemicals Corporation | Ruthenium and osmium catalysts |
US6107420A (en) * | 1998-07-31 | 2000-08-22 | California Institute Of Technology | Thermally initiated polymerization of olefins using Ruthenium or osmium vinylidene complexes |
US20020177710A1 (en) * | 2001-03-23 | 2002-11-28 | California Institute Technology; Cymetech, Llc | Hexacoordinated ruthenium or osmium metal carbene metathesis catalysts |
US6803429B2 (en) * | 2001-03-30 | 2004-10-12 | California Institute Of Technology | Selective ring-opening cross-metathesis of cycloolefins |
US6884859B2 (en) * | 2001-08-29 | 2005-04-26 | California Institute Of Technology | Ring-opening metathesis polymerization of bridged bicyclic and polycyclic olefins containing two or more heteroatoms |
Cited By (67)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080009598A1 (en) * | 1998-04-06 | 2008-01-10 | Degussa Ag | Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
US7378528B2 (en) * | 1998-04-06 | 2008-05-27 | Evonik Degussa Gmbh | Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
US20080207911A1 (en) * | 1998-04-06 | 2008-08-28 | Evonik Degussa Gmbh | Alkylidene complexes of ruthenium containing n-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
US8153810B2 (en) | 1998-04-06 | 2012-04-10 | Evonik Degussa Gmbh | Alkylidene complexes of ruthenium containing N-heterocyclic carbene ligands; use as highly active, selective catalysts for olefin metathesis |
US7960599B2 (en) | 2003-01-13 | 2011-06-14 | Elevance Renewable Sciences, Inc. | Method for making industrial chemicals |
US20070270621A1 (en) * | 2003-01-13 | 2007-11-22 | Millis James R | Method for Making Industrial Chemicals |
KR100607030B1 (ko) | 2004-03-26 | 2006-08-01 | 롬 앤드 하스 캄파니 | 올레핀 중합 촉매 및 중합 공정 |
US20090048459A1 (en) * | 2006-01-10 | 2009-02-19 | Michael John Tupy | Method of making hydrogenated metathesis products |
US8115021B2 (en) | 2006-01-10 | 2012-02-14 | Elevance Renewable Sciences, Inc. | Method of making hydrogenated metathesis products |
US8067623B2 (en) | 2006-07-12 | 2011-11-29 | Elevance Renewable Sciences, Inc. | Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like |
US9139605B2 (en) | 2006-07-13 | 2015-09-22 | Elevance Renewable Sciences, Inc. | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
US9255117B2 (en) | 2006-07-13 | 2016-02-09 | Materia, Inc. | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
US8481747B2 (en) | 2006-07-13 | 2013-07-09 | Elevance Renewable Sciences, Inc. | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
US8067610B2 (en) | 2006-07-13 | 2011-11-29 | Yann Schrodi | Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis |
US20090264672A1 (en) * | 2006-10-13 | 2009-10-22 | Elevance Renewable Sciences, Inc. | Methods of making organic compounds by metathesis |
US8569560B2 (en) | 2006-10-13 | 2013-10-29 | Elevance Renewable Sciences, Inc. | Synthesis of terminal alkenes from internal alkenes via olefin metathesis |
US20100145086A1 (en) * | 2006-10-13 | 2010-06-10 | Elevance Renewable Sciences, Inc. | Synthesis of Terminal Alkenes From Internal Alkenes Via Olefin Metathesis |
US9120742B2 (en) | 2006-10-13 | 2015-09-01 | Elevance Renewable Sciences, Inc. | Methods of making organic compounds by metathesis |
US8895771B2 (en) | 2006-10-13 | 2014-11-25 | Elevance Renewable Sciences, Inc. | Methods of making organic compounds by metathesis and hydrocyanation |
US10906861B2 (en) | 2006-10-13 | 2021-02-02 | Wilmar Trading Pte Ltd | Methods of making organic compounds by metathesis |
US8501973B2 (en) | 2006-10-13 | 2013-08-06 | Elevance Renewable Sciences, Inc. | Synthesis of terminal alkenes from internal alkenes via olefin metathesis |
US20100197920A1 (en) * | 2007-06-20 | 2010-08-05 | Agency For Science, Technology And Research | N-heterocyclic carbene metallacycle catalysts and methods |
US8492552B2 (en) | 2007-06-20 | 2013-07-23 | Agency For Science, Technology And Research | N-heterocyclic carbene metallacycle catalysts and methods |
WO2009142535A1 (fr) | 2008-05-22 | 2009-11-26 | Общество С Ограниченной Ответственностью "Объединённый Центр Исследований И Разработок" | Catalyseur de polymérisation à métathèse de dicyclopentadiène |
CN102317298A (zh) * | 2009-02-18 | 2012-01-11 | 汉高公司 | 可热转换的钌引发剂 |
EP2398814A4 (fr) * | 2009-02-18 | 2013-02-20 | Henkel Corp | Amorceurs à base de ruthénium commutables thermiquement |
EP2398814A2 (fr) * | 2009-02-18 | 2011-12-28 | Henkel Corporation | Amorceurs à base de ruthénium commutables thermiquement |
US8403044B2 (en) | 2009-05-05 | 2013-03-26 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
US20100282467A1 (en) * | 2009-05-05 | 2010-11-11 | Stepan Company | Sulfonated internal olefin surfactant for enhanced oil recovery |
US8846938B2 (en) | 2009-05-07 | 2014-09-30 | Umicore Ag & Co. Kg | Method for preparation of ruthenium-based metathesis catalysts with chelating alkylidene ligands |
US9562116B2 (en) | 2009-05-07 | 2017-02-07 | Umicore Ag & Co. Kg | Method for preparation of ruthenium-based metathesis catalysts with chelating alkylidene ligands |
WO2011005136A1 (fr) | 2009-07-09 | 2011-01-13 | Общество С Ограниченной Ответственностью "Объединённый Центр Исследований И Разработок" | Procédé de production de polydicyclopentadiène et matériaux le contenant |
WO2011043893A2 (fr) * | 2009-10-08 | 2011-04-14 | The Regents Of The University Of California | Catalyseurs moléculaires métal-oxo permettant de générer de l'hydrogène à partir d'eau |
WO2011043893A3 (fr) * | 2009-10-08 | 2011-08-04 | The Regents Of The University Of California | Catalyseurs moléculaires métal-oxo permettant de générer de l'hydrogène à partir d'eau |
WO2011149388A1 (fr) * | 2010-05-27 | 2011-12-01 | Закрытое Акционерное Общество "Сибур Холдинг" | Catalyseur à base de ruthénium de la polymérisation par métathèse de dicylcopentadiène (et variantes) et procédé de production de polycylcopentadiène (et variantes) |
US20140005338A1 (en) * | 2011-03-08 | 2014-01-02 | Zeon Corporation | Polymerizable composition, resin shaped article, and laminate |
US8993819B2 (en) | 2011-07-12 | 2015-03-31 | Basf Se | Process for preparing cycloheptene |
EP2742074A4 (fr) * | 2011-08-12 | 2015-04-01 | Exxonmobil Chem Patents Inc | Polymères préparés par ouverture de cycle/métathèse croisée |
EP2742074A1 (fr) * | 2011-08-12 | 2014-06-18 | ExxonMobil Chemical Patents Inc. | Polymères préparés par ouverture de cycle/métathèse croisée |
US9181360B2 (en) | 2011-08-12 | 2015-11-10 | Exxonmobil Chemical Patents Inc. | Polymers prepared by ring opening / cross metathesis |
US8987531B2 (en) | 2012-03-05 | 2015-03-24 | California Institute Of Technology | Syntheses of Z-olefin-containing lepidopteran insect pheromones |
WO2013134192A1 (fr) * | 2012-03-05 | 2013-09-12 | California Institute Of Technology | Synthèses de phéromones d'insectes lépidoptères contenant de l'olefine z |
US20160185897A1 (en) * | 2013-02-27 | 2016-06-30 | Materia, Inc. | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
US9598531B2 (en) * | 2013-02-27 | 2017-03-21 | Materia, Inc. | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
KR102211385B1 (ko) | 2013-02-27 | 2021-02-03 | 마터리아 인코포레이티드 | 금속 카르벤 올레핀 복분해 2종 촉매 조성물 |
EP2961778A4 (fr) * | 2013-02-27 | 2016-10-05 | Materia Inc | Composition comprenant deux catalyseurs de métathèse d'oléfines de type carbène métallique |
US20140357820A1 (en) * | 2013-02-27 | 2014-12-04 | Materia, Inc. | Olefin metathesis catalyst compositions comprising at least two metal carbene olefin metathesis catalysts |
KR20150122208A (ko) * | 2013-02-27 | 2015-10-30 | 마터리아 인코포레이티드 | 금속 카르벤 올레핀 복분해 2종 촉매 조성물 |
WO2014134333A1 (fr) | 2013-02-27 | 2014-09-04 | Materia, Inc. | Composition comprenant deux catalyseurs de métathèse d'oléfines de type carbène métallique |
US9751975B2 (en) | 2013-07-03 | 2017-09-05 | Materia, Inc. | Liquid molding compositions |
EA032286B1 (ru) * | 2013-07-03 | 2019-05-31 | Материа, Инк. | Жидкие формовочные композиции |
WO2015003147A1 (fr) * | 2013-07-03 | 2015-01-08 | Materia, Inc. | Compositions à mouler liquides |
CN105492489A (zh) * | 2013-07-03 | 2016-04-13 | 马特里亚公司 | 液体模制组合物 |
US9382354B2 (en) | 2013-11-22 | 2016-07-05 | Exxonmobil Chemical Patents Inc. | Polyesters containing polyolefin arms |
WO2015076958A1 (fr) * | 2013-11-22 | 2015-05-28 | Exxonmobil Chemical Patents Inc. | Nouveaux polyesters contenant des bras polyoléfiniques |
WO2015115939A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur de polymérisation par métathèse de dicyclopentadiène et procédé de production |
WO2015115938A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur au ruthénium de polymérisation par métathèse de dicyclopentadiène sous forme de complexe cationique et procédé de production |
WO2015115937A1 (fr) * | 2014-01-29 | 2015-08-06 | Открытое акционерное общество "Нефтяная компания "Роснефть" | Catalyseur de polymérisation par métathèse de dicyclopentadiène sous forme de complexe de ruthénium, et procédé de fabrication |
RU2560151C1 (ru) * | 2014-01-29 | 2015-08-20 | Открытое акционерное общество "Нефтяная компания Роснефть" | Рутениевый катализатор метатезисной полимеризации дициклопентадиена в форме катионного комплекса и способ его получения |
WO2017053690A1 (fr) * | 2015-09-24 | 2017-03-30 | Materia, Inc. | Catalyseurs de métathèse d'oléfines de type carbène métallique |
US10501488B2 (en) | 2015-09-24 | 2019-12-10 | Umicore Ag & Co. Kg | Metal carbene olefin metathesis catalysts |
WO2017100585A1 (fr) * | 2015-12-10 | 2017-06-15 | Materia, Inc. | Catalyseurs de métathèse d'oléfines |
US10857530B2 (en) | 2015-12-10 | 2020-12-08 | Umicore Ag & Co. Kg | Olefin metathesis catalysts |
CN114106057A (zh) * | 2016-10-19 | 2022-03-01 | 优美科股份公司及两合公司 | Ru亚烷基络合物的合成与表征 |
WO2020201314A1 (fr) | 2019-04-02 | 2020-10-08 | Apeiron Synthesis Spolka Akcyjna | Nouvelle utilisation de complexes métalliques ayant des ligands organiques pour activer des (pré)catalyseurs de ruthénium pour la métathèse d'oléfines |
WO2021242636A1 (fr) | 2020-05-29 | 2021-12-02 | Exxonmobil Chemical Patents Inc. | Procédés de production d'oléfines cycliques à partir de polymères et leur re-polymérisation |
CN111777647A (zh) * | 2020-07-31 | 2020-10-16 | 山东京博中聚新材料有限公司 | 一种共轭二烯烃聚合物中碳-碳双键的连续氢化生产装置和方法 |
Also Published As
Publication number | Publication date |
---|---|
US20150141603A1 (en) | 2015-05-21 |
WO2005094345A3 (fr) | 2006-06-22 |
EP1735352B1 (fr) | 2019-08-21 |
WO2005094345A2 (fr) | 2005-10-13 |
JP5622711B2 (ja) | 2014-11-12 |
EP1735352A2 (fr) | 2006-12-27 |
JP2012082435A (ja) | 2012-04-26 |
US20130296511A1 (en) | 2013-11-07 |
AU2005228434A1 (en) | 2005-10-13 |
MXPA06011302A (es) | 2007-01-16 |
US8871879B2 (en) | 2014-10-28 |
PL1735352T3 (pl) | 2020-06-29 |
BRPI0509322A (pt) | 2007-09-04 |
EP1735352A4 (fr) | 2011-05-11 |
JP2007530706A (ja) | 2007-11-01 |
US9238709B2 (en) | 2016-01-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9238709B2 (en) | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand | |
US7598330B2 (en) | Cross-metathesis of olefins directly substituted with an electron-withdrawing group using transition metal carbene catalysts | |
EP1765839B1 (fr) | Complexes carbènes de métaux de transition contenant un substituant cationique, utilisés en tant que catalyseurs des réactions de métathèse des oléfines | |
KR100497024B1 (ko) | 고복분해 활성 루테늄 및 오스뮴 금속 카르벤 착화합물 | |
AU2012206966A1 (en) | Z-selective olefin metathesis catalysts and their synthetic procedure | |
WO2012097379A2 (fr) | Catalyseurs pour métathèse d'oléfines z-sélective et leur procédure de synthèse | |
US11065609B2 (en) | Synthesis and characterization of metathesis catalysts | |
US11173476B2 (en) | Metathesis catalysts | |
WO2020109217A2 (fr) | Composés organométalliques | |
AU2011205218B2 (en) | Latent, high-activity olefin metathesis catalysts containing an N-heterocyclic carbene ligand | |
CN101090915A (zh) | 含有n-杂环卡宾配体的潜伏的高活性烯烃置换催化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MATERIA, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:UNG, THAY;SCHRODI, YANN;TRIMMER, MARK S.;REEL/FRAME:018517/0869;SIGNING DATES FROM 20060403 TO 20060602 Owner name: CALIFORNIA INSTITUTE OF TECHNOLOGY, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HEJL, ANDREW;SANDERS, DANIEL;GRUBBS, ROBERT H.;REEL/FRAME:018518/0023;SIGNING DATES FROM 20060402 TO 20060828 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- AFTER EXAMINER'S ANSWER OR BOARD OF APPEALS DECISION |
|
AS | Assignment |
Owner name: NATIONAL INSTITUTES OF HEALTH, MARYLAND Free format text: CONFIRMATORY LICENSE;ASSIGNOR:CALIFORNIA INSTITUTE OF TECHNOLOGY;REEL/FRAME:048640/0095 Effective date: 20190319 |