FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W3189810366> ?p ?o ?g. }

• W3189810366 endingPage "12856" @default.
• W3189810366 startingPage "12847" @default.
• W3189810366 abstract "Metal-catalyzed hydrosilylation of alkynes is an ideal atom-economic method to prepare vinylsilanes that are useful reagents in the organic synthesis and silicone industry. Although great success has been made in the preparation of β-vinylsilanes by metal-catalyzed hydrosilylation reactions of alkynes, reported metal-catalyzed reactions for the synthesis of α-vinylsilanes suffer from narrow substrate scope and/or poor selectivity. Herein, we present selective Markovnikov hydrosilylation reactions of terminal alkynes with tertiary silanes using a dicobalt carbonyl N-heterocyclic carbene (NHC) complex [(IPr)2Co2(CO)6] (IPr = 1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidene) as catalyst. This cobalt catalyst effects the hydrosilylation of both alkyl- and aryl-substituted terminal alkynes with a variety of tertiary silanes with good functional group compatibility, furnishing α-vinylsilanes with high yields and high α/β selectivity. Mechanistic study revealed that the stoichiometric reactions of [(IPr)2Co2(CO)6] with PhC≡CH and HSiEt3 can furnish the dinuclear cobalt alkyne and mononuclear cobalt silyl complexes [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)3], [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)2(IPr)], and [(IPr)Co(CO)3(SiEt3)], respectively. Both dicobalt bridging alkyne complexes can react with HSiEt3 to yield α-triethylsilyl styrene and effect the catalytic Markovnikov hydrosilylation reaction. However, the mono(NHC) dicobalt complex [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)3] exhibits higher catalytic activity over the di(NHC)-dicobalt complexes. The cobalt silyl complex [(IPr)Co(CO)3(SiEt3)] is ineffective in catalyzing the hydrosilylation reaction. Deuterium labeling experiments with PhC≡CD and DSiEt3 indicates the syn-addition nature of the hydrosilylation reaction. The absence of deuterium scrambling in the hydrosilylation products formed from the catalytic reaction of PhC≡CH with a mixture of DSiEt3 and HSi(OEt)3 hints that mononuclear cobalt species are less likely the in-cycle species. These observations, in addition to the evident of nonsymmetric Co2C2-butterfly core in the structure of [(IPr)(CO)2Co(μ-η2:η2-HCCPh)Co(CO)3], point out that mono(IPr)-dicobalt species are the genuine catalysts for the cobalt-catalyzed hydrosilylation reaction and that the high α selectivity of the catalytic system originates from the joint play of the dicobalt carbonyl species to coordinate alkynes in the Co(μ-η2:η2-HCCR')Co mode and the steric demanding nature of IPr ligand." @default.
• W3189810366 created "2021-08-16" @default.
• W3189810366 creator A5010215438 @default.
• W3189810366 creator A5010692353 @default.
• W3189810366 creator A5016806564 @default.
• W3189810366 creator A5049078993 @default.
• W3189810366 creator A5085872494 @default.
• W3189810366 creator A5087789746 @default.
• W3189810366 date "2021-08-04" @default.
• W3189810366 modified "2023-10-16" @default.
• W3189810366 title "Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation" @default.
• W3189810366 cites W1989908861 @default.
• W3189810366 cites W1993855951 @default.
• W3189810366 cites W1997857531 @default.
• W3189810366 cites W1999358670 @default.
• W3189810366 cites W2006487571 @default.
• W3189810366 cites W2011707142 @default.
• W3189810366 cites W2013219773 @default.
• W3189810366 cites W2017239055 @default.
• W3189810366 cites W2022488242 @default.
• W3189810366 cites W2027458599 @default.
• W3189810366 cites W2034530074 @default.
• W3189810366 cites W2044311286 @default.
• W3189810366 cites W2050180844 @default.
• W3189810366 cites W2058978512 @default.
• W3189810366 cites W2064400109 @default.
• W3189810366 cites W2067525145 @default.
• W3189810366 cites W2071732510 @default.
• W3189810366 cites W2081660555 @default.
• W3189810366 cites W2098106988 @default.
• W3189810366 cites W2118210031 @default.
• W3189810366 cites W2124510448 @default.
• W3189810366 cites W2167013002 @default.
• W3189810366 cites W2170228822 @default.
• W3189810366 cites W2301090685 @default.
• W3189810366 cites W2312674207 @default.
• W3189810366 cites W2404169337 @default.
• W3189810366 cites W2495361167 @default.
• W3189810366 cites W2509035035 @default.
• W3189810366 cites W2558354261 @default.
• W3189810366 cites W2559442279 @default.
• W3189810366 cites W2581880278 @default.
• W3189810366 cites W2593209921 @default.
• W3189810366 cites W2803624660 @default.
• W3189810366 cites W2894158568 @default.
• W3189810366 cites W2895680839 @default.
• W3189810366 cites W2897439472 @default.
• W3189810366 cites W2934545677 @default.
• W3189810366 cites W2947338987 @default.
• W3189810366 cites W2950260188 @default.
• W3189810366 cites W2951786214 @default.
• W3189810366 cites W2958407588 @default.
• W3189810366 cites W2971952023 @default.
• W3189810366 cites W3004273252 @default.
• W3189810366 cites W3043415759 @default.
• W3189810366 cites W3087702676 @default.
• W3189810366 cites W3119770516 @default.
• W3189810366 cites W3119820467 @default.
• W3189810366 cites W4239321948 @default.
• W3189810366 cites W4239635116 @default.
• W3189810366 cites W4376522421 @default.
• W3189810366 doi "https://doi.org/10.1021/jacs.1c06583" @default.
• W3189810366 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/34347477" @default.
• W3189810366 hasPublicationYear "2021" @default.
• W3189810366 type Work @default.
• W3189810366 sameAs 3189810366 @default.
• W3189810366 citedByCount "31" @default.
• W3189810366 countsByYear W31898103662021 @default.
• W3189810366 countsByYear W31898103662022 @default.
• W3189810366 countsByYear W31898103662023 @default.
• W3189810366 crossrefType "journal-article" @default.
• W3189810366 hasAuthorship W3189810366A5010215438 @default.
• W3189810366 hasAuthorship W3189810366A5010692353 @default.
• W3189810366 hasAuthorship W3189810366A5016806564 @default.
• W3189810366 hasAuthorship W3189810366A5049078993 @default.
• W3189810366 hasAuthorship W3189810366A5085872494 @default.
• W3189810366 hasAuthorship W3189810366A5087789746 @default.
• W3189810366 hasConcept C155647269 @default.
• W3189810366 hasConcept C161790260 @default.
• W3189810366 hasConcept C178790620 @default.
• W3189810366 hasConcept C185592680 @default.
• W3189810366 hasConcept C188027245 @default.
• W3189810366 hasConcept C2778024649 @default.
• W3189810366 hasConcept C2778183973 @default.
• W3189810366 hasConcept C2778421718 @default.
• W3189810366 hasConcept C515602321 @default.
• W3189810366 hasConcept C59759590 @default.
• W3189810366 hasConcept C98939719 @default.
• W3189810366 hasConceptScore W3189810366C155647269 @default.
• W3189810366 hasConceptScore W3189810366C161790260 @default.
• W3189810366 hasConceptScore W3189810366C178790620 @default.
• W3189810366 hasConceptScore W3189810366C185592680 @default.
• W3189810366 hasConceptScore W3189810366C188027245 @default.
• W3189810366 hasConceptScore W3189810366C2778024649 @default.
• W3189810366 hasConceptScore W3189810366C2778183973 @default.
• W3189810366 hasConceptScore W3189810366C2778421718 @default.
• W3189810366 hasConceptScore W3189810366C515602321 @default.
• W3189810366 hasConceptScore W3189810366C59759590 @default.

• next