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

Claire J Carmalt; Anne C Newport; Shane A O'Neill; Ivan P Parkin; Andrew J P White; David J Williams

doi:10.1021/ic049013u

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

Inorg Chem. 2005 Feb 7;44(3):615-9. doi: 10.1021/ic049013u.

Authors

Claire J Carmalt¹, Anne C Newport, Shane A O'Neill, Ivan P Parkin, Andrew J P White, David J Williams

Affiliation

¹ Christopher Ingold Laboratories, Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom. c.j.carmalt@ucl.ac.uk

PMID: 15679392
DOI: 10.1021/ic049013u

Abstract

The mono(guanidinato) complex [Ti(NMe2)2Cl{i-PrNC[N(SiMe3)2]N-i-Pr}] (1) was prepared by reaction of [Ti(NMe2)2Cl2] with 1 or 2 equiv of the lithium guanidinate salt [Li{i-PrNC[N(SiMe3)2]N-i-Pr}]. Compound 1 has been characterized by X-ray crystallography. Treatment of TiCl4 with 2 equiv of [Li{i-PrNC[N(SiMe3)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, [TiCl2{i-PrNC[N(SiMe3)2]N-i-Pr}{i-PrNC(N=CMe2)N-i-Pr}] (2) and [TiCl2{i-PrNC[N(SiMe3)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 [TiCl2{i-PrNC(NMe2)N-i-Pr}] (4) at 600 degrees C results in thin films of titanium carbonitride.