Theoretical investigation of substitutent effects on the silicon-metal bond for a series of transition metal-substituted base-stabilized silylene complexes

摘要

Hartree-Fock ab initio calculations were used to investigate the effects of various silicon substituents on ~he silicon-ruthenium bond for four transition metal-substituted base-stabilized silylene complexes. To provide comparison information, one silyl complex, Cp*(PMe_3)_2Ru-Si[S(Tol-p )]_3, and four base-free silylene complexes ([Cp*(PMe_3hRu=SiMe_2]BPh_4, Cp.(PMe_3)_2Ru=Si[S(Tol-p)][Os(CO)_4]' a bis(silylene)nickel compound and [trans-(P(Cy_3)_2(H)Pt=Si(SEt)_2]BPh_4) were also studied. Results of the calculations indicate that the order of promotion of silylene character for base groups is NCMe > OTf? S(Tol-p). Of those considered, the best substituent group in terms of transition metal-silicon double bond promotion is methyl followed by triflate. The worst group with respect to this property is S(T ol-p ).