17106-33-1Relevant academic research and scientific papers
Highly selective hydrosilylation of olefins and acetylenes by platinum(0) complexes bearing bulky N-heterocyclic carbene ligands
Zak,Bo?t,Kubicki,Pietraszuk
supporting information, p. 1903 - 1910 (2018/02/17)
Platinum complexes bearing bulky N-heterocyclic carbene (NHC) ligands, i.e., [Pt(IPr?)(dvtms)] (where, IPr? = 1,3-bis{2,6-bis(diphenylmethyl)-4-methylphenyl}imidazol-2-ylidene) and [Pt(IPr?OMe)(dvtms)] (where, IPr?OMe = 1,3-bis{2,6-bis(diphenylmethyl)-4-m
Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation
Vijaykumar, Gonela,Pariyar, Anand,Ahmed, Jasimuddin,Shaw, Bikash Kumar,Adhikari, Debashis,Mandal, Swadhin K.
, p. 2817 - 2825 (2018/03/21)
In this report, a ligand-redox assisted catalytic hydrosilylation has been investigated. A phenalenyl ligand coordinated nickel complex has been utilized as an electron reservoir to develop a base metal-assisted catalyst, which very efficiently hydrosilylates a wide variety of olefin substrates under ambient conditions. A mechanistic investigation revealed that a two-electron reduced phenalenyl based biradical nickel complex plays the key role in such catalysis. The electronic structure of the catalytically active biradical species has been interrogated using EPR spectroscopy, magnetic susceptibility measurements, and electronic structure calculations using a DFT method. Inhibition of the reaction by a radical quencher, as well as the mass spectrometric detection of two intermediates along the catalytic loop, suggest that a single electron transfer from the ligand backbone initiates the catalysis. The strategy of utilising the redox reservoir property of the ligand ensures that the nickel is not promoted to an unfavorable oxidation state, and the fine tuning between the ligand and metal redox orbitals elicits smooth catalysis.
Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si?H Activation
Zhou, Rong,Goh, Yi Yiing,Liu, Haiwang,Tao, Hairong,Li, Lihua,Wu, Jie
supporting information, p. 16621 - 16625 (2017/12/13)
Although there has been significant progress in the development of transition-metal-catalyzed hydrosilylations of alkenes over the past several decades, metal-free hydrosilylation is still rare and highly desirable. Herein, we report a convenient visible-
Mode of activation of cobalt(II) amides for catalytic hydrosilylation of alkenes with tertiary silanes
Liu, Yang,Deng, Liang
supporting information, p. 1798 - 1801 (2017/02/15)
Cobalt(II) complexes capable of catalyzing alkene hydrosilylation in the absence of external activators are rarely known, and their activation mode has remained poorly understood. We present here that cobalt(II) amide complexes, [Co(N(SiMe3)2)2] and its NHC adducts [(NHC)Co(N(SiMe3)2)2] (NHC = N-heterocyclic carbene), are effective catalysts for the hydrosilylation of alkenes with tertiary silanes. Mechanistic studies revealed that cobalt(II) amides can react with hydrosilane to form cobalt(I) species, silylamide, and hydrogen, which serves as the entry to the genuine catalytically active species, presumably cobalt(I) species, for the cobalt-catalyzed hydrosilylation reaction.
METHOD FOR PRODUCING ORGANOSILICON COMPOUND AND CATALYST COMPOSITION
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Paragraph 0031; 0032, (2016/12/01)
PROBLEM TO BE SOLVED: To provide a method for producing an organosilicon compound by the hydrosilylation reaction of alkenes or alkynes using a new catalyst. SOLUTION: There is provided a method for producing an organosilicon compound in which a nickel complex compound represented by the following formula and a borane compound such as tri(pentafluorophenyl)borane or a hydride reducing agent such as sodium triethylhydroborate are blended in a reaction solution in the hydrosilylation reaction of alkenes such as 1-octene and butadiene or alkynes. (R1 each independently represents H or a hydrocarbon group having 1 to 15 carbon atoms substituted/unsubstituted with at least one atom selected from N, O, S or a halogen atom.) COPYRIGHT: (C)2016,JPOandINPIT
Efficient Pd(O)-catalyzed hydrosilylation of alkynes with triorganosilanes
Motoda, Dai,Shinokubo, Hiroshi,Oshima, Koichiro
, p. 1529 - 1531 (2007/10/03)
An electron-rich Pd(0) complex, a Pd2(dba)3·CHCl3- tricyclohexylphosphine combination catalyzes highly efficient hydrosilylation of alkynes at room temperature with Ph3SiH or Ph2MeSiH without solvents
HOMOGENEOUS CATALYSIS. IX. HYDROSILYLATION USING TRIS(PENTANEDIONATO)RHODIUM(III)-TRIALKYLALUMINIUM AS CATALYST
Cornish, Andrew J.,Lappert, Michael F.
, p. 153 - 168 (2007/10/02)
The two component (Ziegler) catalyst -AlEt3 (or an analogue with an alternative cocatalyst) has been investigated for the hydrosilylation by SiHX3 of alkynes, dienes, alkenes, styrene, or allylbenzene at 60 deg C.Terminal alkynes did not yield adducts, but internal alkynes RCCR' gave products of cis-addition with SiHEt3 or SiHEt2Me (but not SiH(OEt)3), without regiospecificity for the case of R R'.Acyclic dienes gave 1/1 adducts with SiHX3 (X = Me, Et, OEt or OSiMe3; but not X = Ph), predominantly (or, for penta-1,3-diene, exclusively) the products of 1,4-addition.Among cyclic dienes, only cyclohexa-1,3- (or -1,4)-diene was hydrosilylated with SiHEt3 to yield cyclohex-2-enyltriethylsilane; cycloocta-1,3-diene was merely rearranged to the 1,5-isomer, norbornadiene was polymerised, and no reaction was observed with 2,5-dimethylhexa-2,4-diene.Internal straight-chain alkenes RR'C=CHR'', RR'C=CR''R''', or cyclohexene proved unreactive; however disubstituted olefins RCH=CHR' gave the terminal (isomerised) 1/1-adducts, e.g., n-C5H11SiEt3 from MeCH=CHEt and SiHEt3.Likewise terminal alkenes RCH=CH2 gave RCH2CH2SiX3 (X = Ph or OEt) or (X = Et) a mixture of isomeric 1/1 adducts.With styrene and SiHEt3, or to a lesser extent SiH(OR)3 (R = Me or Et), the dehydrogenative hydrosilylated material, the vinylsilane PhCH=CHSiX3, was the principial product with isomeric 1/1 adduct byproducts; with allylbenzene, likewise, PhCH2CH=CHSiX3 was a significant, but less important, component of the reaction mixture.Mechanistic pathways are proposed; for the dehydrogenative hydrosilylation of styrene, crucial steps are styrene insertion into a RhIII-SiX3 bond and a subsequent intramolecular hydrogen transfer, which are consistent with both a labelling experiment using SiDEt3 and the lack of dehydrogenation (under the reaction conditions) of PhCH2CH2SiEt3.
