Abstract
Publisher Summary This chapter discusses the η 2 coordination of Si–H σ bonds to transition metals. The first complexes of type Cp(OC) 2 Mn(H)SiR 3 (R = Ph, C1) were prepared by Jetz and Graham by the photochemical reaction of Cp(OC) 3 Mn with the corresponding silanes HSiR 3 . From the very beginning, it was realized that some properties of the complexes CP(OC) 2 Mn(H)SiR 3 are different from those of other hydrido silyl complexes and that the silane moiety was bonded in an unusual way. The first structural evidence for an Si–H interaction in complexes of the type Cp(OC) 2 Mn(H)SiR 3 was obtained for the SiPh 3 derivative. On the basis of the structural data, the two CO ligands in the dicarbonyl complexes would be expected to be inequivalent. Photoelectron (PE) spectra provide direct and quantitative information on the electron distribution within a compound. Recent investigation of the PE spectra of a number of MeCp(OC) 2 Mn(H)SiR 3 derivatives confirmed the theoretical results. Both the chemical behavior and crystal structure of Cp(OC) 2 Re(H)SiPh 3 indicate that, contrary to the corresponding manganese complexes, there is no metal–hydrogen–silicon three-center bond.
Published Version
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