Transition-Metal Silyl Complexes and Chemistry in the Reactions of Silanes with Transition-Metal Complexes

Studies from the authors' group of early-transition-metal silyl complexes and pathways in the reactions of silanes with transition-metal complexes are reviewed. Cyclopentadienyl-free, group 4 alkyl silyl, group 5 alkylidene silyl, group 6 alkylidyne silyl, and groups 4 and 5 amide and imide silyl complexes have been prepared and characterized. In the reactions of silanes with alkylidene and amide complexes, the MCH− π bonds and d−p π bonds in MNR2 were found to attack Si in silanes. The mechanistic studies here help in understanding the formation of mixtures of TiN and Si3N4 from the reactions of Ti(NMe2)4 and SiH4 as microelectronic diffusion barrier materials.