Synthesis of titanium(IV) guanidinate complexes and the formation of titanium carbonitride via low-pressure chemical vapor deposition

The mono(guanidinato) complex [Ti(NMe(2))(2)Cl{i-PrNC[N(SiMe(3))(2)]N-i-Pr}] (1) was prepared by reaction of [Ti(NMe(2))(2)-Cl(2)] with 1 or 2 equiv of the lithium guanidinate salt [Li{i-PrNC[N(SiMe(3))(2)]N-i-Pr}]. Compound 1 has been characterized by X-ray crystallography. Treatment of TiCl(4) With 2 equiv of [Li{i-PrNC[N(SiMe(3))(2)]N-i-Pr}] resulted in the formation of dark red crystals. X-ray crystallography showed that these crystals consist of a 70:30 mixture of two bis(guanidinato) complexes, namely, [TiCl(2){i-PrNC[N(SiMe(3))(2)]N-i-Pr}{i-PrNC(N=CMe(2))N-i-Pr}] (2) and [TiCl(2){i-PrNC[N(SiMe(3))(2)]N-i-Pr}{i-PrNC[N(H)-i-Pr]N-i-Pr}] (3). Both compounds 2 and 3 possess a transformed guanidinate ligand. Low-pressure chemical vapor deposition of either compound 1 or [TiCl(2){i-PrNC(NMe(2))N-i-Pr}] (4) at 600 degreesC results in thin films of titanium carbonitride.