Journal
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
Volume 243, Issue 2, Pages 253-257Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.molcata.2005.08.032
Keywords
hydrosilylation; metallocene catalysis; regio-selectivity; branched silane; 2,1-addition
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Metallocene complexes of type Cp'2MCH(TMS)(2) (Cp' =eta(5)-Me5C5, M = Y, Sm), Me2SiCp2SmCH(TMS)(2) (Cp =eta(5)-Me4C5) catalyze rapid and clean hydrosilylation of CH2=CH-SiMe2R (R = Me, Ph, NMe2, O'Bu) with PhSiH3. The distribution of 1,2-addition product versus 2, 1-addition product was found to be sensitive to both catalysts and substrates. Generation of 2, 1-addition product can best be achieved by use of more sterically accessible catalysts as well as substrates containing tethering functional groups. A. four-centered transition state is invoked to explain these effects. [GRAPHICS] (c) 2005 Elsevier B.V. All rights reserved.
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