76261-67-1Relevant articles and documents
Copper-catalyzed hydrosilylation with a bowl-shaped phosphane ligand: Preferential reduction of a bulky ketone in the presence of an aldehyde
Fujihara, Tetsuaki,Semba, Kazuhiko,Terao, Jun,Tsuji, Yasushi
supporting information; experimental part, p. 1472 - 1476 (2010/05/02)
Chemical Equation Presented Hollywood bowl: A highly active copper catalyst with a bowl-shaped phosphane (bsp) ligand was used in the hydrosilylation reaction of bulky ketones. The preferential reduction of a bulky ketone in the presence of an unprotected aldehyde is unprecedented.
Kinetics of hydrosilylation of tert-butylphenylketone by diphenylsilane catalysed by (1+)ClO4(1-)
Kolb, Ivan,Heftlejs, Jiri
, p. 2224 - 2239 (2007/10/02)
Kinetic analysis of the title reaction has been made by the method of initial reaction rates.On the basis of the rate data, kinetic isotope effect and spectroscopic study of the reaction of the organosilicon hydride with the catalyst, the reaction model was proposed involving the following steps: the displacement of the diene by reaction with the silicon hydride to form a rhodium-arene complex in an induction period of the hydrosilylation, the oxidative addition of the organosilicon hydride to the rhodium-arene complex, followed by the interaction of the ketone with the silylhydridorhodium (III) species in the rate determining step.The process is characterized by the folowing activation parameters: ΔU% = 54.5 +/- 8.5 kJ*mol-1 and ΔS% = -88 +/- 25 J*mol-1*K-1.The significant role of the entropic factor was supported by the analysis of the temperature dependence of the asymmetric efficiency of the catalyst.