Synthesis of zirconium guanidinate complexes and the formation of zirconium carbonitride via low pressure CVD

Thin films of zirconium carbonitride have been deposited on glass at 600 °C from two novel guanidinate precursors: [ZrCp'{¿2-(iPrN)2CNMe2}2Cl] (1) and [ZrCp'2{¿2-(iPrN)2CNMe2}Cl] (2) (Cp' ) monomethylcyclopentadienyl). Both compounds 1 and 2 were structurally characterized by X-ray crystallography. The films grown via low pressure chemical vapor deposition (LPCVD) from compound 1 were mirrorlike with a red-brown sheen whereas those from 2 were gray. Chlorine was present in the films although the levels were no higher than 3 at.%. These two compounds clearly show how the coordination environment around the metal center affects the composition of the film, as films from 1 were nitrogen rich and those from 2 were carbon rich. The films were uniform, adhesive, abrasion resistant, conformal, and hard, being resistant to scratching with steel and brass scalpels.