The Chloride Effect: Structural Dependence of Ruthenium Silyl Complexes on Phosphorus and Silicon Substituents

The structures for a series of Cp(PR3)2RuSiX3
{PR3 = PMe3, SiX3 = SiCl3, SiMeCl2, SiPhCl2; PR3 =
PMe2Ph, SiX3 = SiCl3} complexes were determined and
compared. The Ru−Si and Si−Cl distances in these
complexes increased when Cl was replaced with Me or
Ph groups and correlated with the observed spectroscopic
properties of these complexes. The structural variations
were explained by d(Ru)−σ*(Si−Cl) π-back-bonding
interactions.