Spontaneous Evolution of Silica-Supported Ti Amide Fragments to Imine and Imido Complexes

Upon prolonged exposure to vacuum, (⋮SiO) 2 Ti(N(CH 2 R) 2 (R = H, ( 1 ), Me ( 2 )) evolves to an N -methylmethylenimine complex ( 3; R = H) or an ethylimido complex ( 5; R = Me). The change in the reaction mechanism depending on the nature of the molecular precursor accounts for the lower level of carbon contamination in TiN films formed from the complex with the higher initial carbon content.