2295-05-8Relevant articles and documents
Jancke et al.
, p. 97,101 (1973)
Catalytic transformations of oligocarbosilanes induced by AlCl3
Chernyavskaya,Aleksinskaya,Zavin,Belokon'
, p. 2147 - 2148 (1997)
Catalytic activation of Si - C bonds in poly(vinyltrimethylsilane) was studied using a model reaction of catalytic transformations of oligocarbosilanes Me3Si(CH2)nSiMe3 (n = 2, 3) in dichlorodimethylsilane in the presence of AlCl3 as an example. The formation of ClMe2Si(CH2)nSiMe3 was established by chromato-mass spectrometry and GLC.
On the mechanism of metal colloid catalyzed hydrosilylation: Proposed explanations for electronic effects and oxygen cocatalysis
Lewis, Larry N.
, p. 5998 - 6004 (2007/10/02)
Several aspects of the platinum-catalyzed hydrosilylation reaction, R3SiH + R′CH=CH2, are described and a mechanism based on the intermediacy of colloids is proposed. New features of this mechanism include (1) formation of a Pt colloid/R3SiH intermediate 2 from the reaction of the Pt colloid 1 and R3SiH, (2) consideration of the olefin as a nucleophile and thus intermediate 2 being an electrophile in this reaction, (3) hydrosilylation dependence on cocatalysis by dioxygen where no O-O bond breakage occurs and dioxygen action to electronically modify 2 by making it more electrophilic, (4) hydrosilylation being but one case of the reactivity of 2 with nucleophiles; the reaction with R″OH where R″ = H or alkyl is discussed. The effect of the electronic nature of the substituents on the rate of hydrosilylation was measured. Electron withdrawing substituents, R, on R3SiH accelerate the rate of addition to olefins, e.g. the rate of addition of (EtO)3SiH to olefins proceeds at a higher rate than the addition of Et3SiH to olefins. Electron donating groups, R′, on R′CH=CH2 greatly accelerate the rate of R3SiH to olefins, e.g. the Et3SiH addition occurs at a faster rate to Me3SiCH=CH2 than to Cl3SiCH=CH2. The relative rate of addition of (EtO)3SiH to a series of para-substituted styrenes was studied which confirmed the trend that higher rates of addition of R3SiH occurs to olefins, R′CH=CH2 with more electron donating substituents, R′. The origin of the cocatalytic effect of dioxygen in hydrosilylation was studied by generating Pt colloid under an atmosphere containing 16O2 and 18O2 and noting that the O-O bond is not broken and reformed under these conditions. It was demonstrated that the proposed intermediate 2 behaves as an electrophile by showing that Me3SiCH2CH=CH2 exchanges with Et3SiH in the presence of Pt to give trapped products based on the rearranged products Me3SiH and Et3SiCH2CH=CH2 in the presence of an electrophile (in this case Pt/Et3SiH). The reaction of water with R3SiH in the presence of a Pt catalyst in commercial silicone foams produces H2, and this reaction is described in the context of hydrosilylation where the water nucleophile replaces the olefin.
Carbanion Rearrangements of ω-Phenyl-ω-(trimethylsilyl)alkyllithium Compounds: Intramolecular Reactions of Benzyltrimethylsilanes with a Carbon-Lithium Bond
Maercker, Adalbert,Stoetzel, Reinhard
, p. 1695 - 1706 (2007/10/02)
ω-Phenyl-ω-(trimethylsilyl)alkyllithium compounds show four out of five theoretically conceivable possibilities for intramolecular stabilization depending on the solvent and on the chain length n.While transmetalation of a methyl group at the silicon atom by a 1,(n+2) proton transfer is observed in any case, the intramolecular 1,n shift of the benzylic proton does only take place with n >/= 4.The main reaction, however for n = 3 and 4 only, is represented by the 1,n trimethylsilyl shift via a cyclic ate complex as an intermediate which partly splits off methyllithium yielding the corresponding silacycloalkane derivatives.In going from diethyl ether to THF as the solvent, the silyl shifts are more accelerated than the proton shifts.In no case, however, a Grovenstein-Zimmermann rearrangement involving phenyl migration took place.Degenerate silyl shifts starting from α-deuterated ω-(trimethylsilyl)alkyllithium compounds could not be detected either.Only by introduction of a second trimethylsilyl group into the 3 position a 1,3-(C -> C)-trimethylsilyl shift is initiated again.
