DFT calculations with the B3LYP functional are carried out on the systems [Cp(PH3)Ir(SiHR2)]+ and [Cp(PH3)Ir(SiR3)]+ (Cp = C5H5, R = H, CH3, SiH3, Cl), which are representative examples of experimental complexes where the silylene ligand can exist. Geometry optimization for the different systems gives a large variety of structures, including the conventional silyl and hydrido silylene isomers, but also other less usual bridged structures, with a variety of groups taking a bridging position. Analysis of the large amount of data, together with those previously reported for [(dhpe)Pt(SiHR2)]+ and [(dhpe)Pt(SiR3)]+ (dhpe = H2P-CH2-CH2-PH2), leads to a better understanding of the general factors governing the relative stabilities of the possible isomeric forms.
Silyl, Hydrido Silylene or Alternative Bonding Modes: The Many Possible Structures of [(C5H5)(PH3)IrX]+ (X = SiHR2 and SiR3; R = H, CH3, SiH3, and Cl)
Organometallics 2006, 25, 4748-4755.