Spontaneous evolution of silica-supported Ti amide fragments to imine and imido complexes

Upon prolonged exposure to vacuum (drop SiO)(2)Ti(N(CH2R)(2) (R = H, (1), M e (2)) evolves to an N-methylmethylenimine complex (3; R = H) or an ethylim ido complex: (5; R = Me). The change in, the reaction mechanism depending o n the nature of the molecular precursor accounts for the lower level of car bon contamination in TiN films formed from the complex with the higher init ial carbon content.