5290-25-5Relevant articles and documents
Mechanistic insights into the hydrosilylation of allyl compounds - Evidence for different coexisting reaction pathways
Gigler, Peter,Drees, Markus,Riener, Korbinian,Bechlars, Bettina,Herrmann, Wolfgang A.,Kuehn, Fritz E.
, p. 1 - 14 (2013/01/14)
The hydrosilylation of allyl compounds is often accompanied by the formation of high amounts of byproducts. The formation processes have not been fully understood so far. In this work, the allyl hydrosilylation mechanism is investigated in detail and experimental and theoretical evidence for multiple, coexisting reaction pathways is provided. Based on earlier reports and the observations during an extensive catalytic study, different pathways, leading to the observed byproducts, were identified and proven by labeling experiments and DFT calculations. Oxidative addition of the silane and the insertion of the allyl compound into the Pt-H bond turned out to be the crucial, selectivity-determining steps within the catalytic cycle. Based on these findings, it should be possible to systematically influence these steps and pave the way to a rational and straightforward design of more selective catalysts.
Effect of catalysts on the reaction of allyl esters with hydrosilanes
Belyakova,Pomerantseva,Efimova,Chernyshev,Storozhenko
experimental part, p. 728 - 733 (2011/01/05)
The reaction of hydrosilylation of allyl esters XOCH 2CH=CH 2 (X = MeCO, CF 3CO, C 3F 7CO) and PhOCH 2CH=CH 2 with hydrosilanes HSiY 3 (Y = Cl, OEt) in the presence of the Speier catalyst, the Speier catalyst with additives, and of various nickel complexes was studied. The catalytic hydrosilylation reaction in the presence of the Speier catalyst is accompanied by the reduction. Additives to the Speier catalyst (vinyltriethoxysilane and some ethers) allow to suppress considerably the reduction reaction. In the presence of the studied nickel complexes mainly reduction and isomerization reactions occurred. The best nickel catalysts of hydrosilylation were the mixtures of NiCl 2 or Ni(acac) 2 with phosphine oxides. In contrast to allyl esters, the hydrosilylation of simple olefins proceeds easier, the content of the product of hydrosilylation in the reaction mixture reaches 94.3%. Pleiades Publishing, Ltd., 2010.
