Catalysis of the Hydrosilation and Bis-Silylation Reactions
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Ab initio electronic structure calculations using RHF, MP2, and CCSD(T) levels of theory have been used to investigate a reaction path for the hydrosilation reaction catalyzed by divalent titanium (modeled by TiH2 and TiCl2). Optimized structures and energies are presented. All levels of theory predict a barrierless reaction path compared to a barrier of at least 55 kcal/mol at the MP2 level for the analogous uncatalyzed reactions. The use of correlated methods (MP2 or CCSD(T)) is required to obtain accurate structures and energies.
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Reprinted (adapted) with permission from ACS Symposium Series, vol. 721, (1999): Transition State Modeling for Catalysis, chapter 10, 128, doi:10.1021/bk-1999-0721.ch010. Copyright 1999 American Chemical Society.