Abstract
The reaction of Cp(PMe3)2RuCH2SiMe3 (1) with (η1-Cp*)SiHCl2 in refluxing toluene produces silyl Cp(PMe3)2RuSiCl2(η1-Cp*) (2) in good yields; Cp(PMe3)2RuSiCl3 (3) is a minor product of this reaction. The Cp* group in 2 is σ-bound to the silicon and is “static” on the NMR time scale at room temperature. The η1-Cp* configuration in 2 was confirmed by a single-crystal X-ray diffraction study. In the structure of 2, a “three-legged piano stool” geometry is observed around ruthenium whereas the silicon adopts a distorted tetrahedral geometry. The η1-Cp* group on silicon is in an anti relationship with one of the phosphines on ruthenium (dihedral angle = 179.5(3)°). Complex 2 exhibits reactions involving chloride substitution, Si−Cp* bond cleavage, and Ru−Si bond cleavage. The reaction of 2 with LiAlH4 produces Cp(PMe3)2RuSiH2(η1-Cp*) (6) in which the η1-Cp* group is more mobile compared to 2. The Si−Cp* bond of 2 is readily cleaved by acid (i.e HCl(g), pyridinium chloride) to give 3 and pentamethylcyclopentadiene. Methanolysis of 2 cleaves the Ru−Si bond and gives the dihydride [Cp(PMe3)2RuH2]Cl in nearly quantitative yields.
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