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Pure Appl. Chem., 2001, Vol. 73, No. 2, pp. 331-335

Reactions of d0 alkylidene and amide complexes with silanes

Jonathan B. Diminnie1, Xiaozhan Liu1, Hu Cai1, Zhongzhi Wu1, Jaime R. Blanton1, Tianniu Chen1, Albert A. Tuinman1, Keith T. Quisenberry1, Catherine E. Vallet2, Ray A. Zuhr3, David B. Beach2, Zhihui Peng4, Yun-Dong Wu4*, Thomas E. Concolino5, Arnold L. Rheingold5 and Ziling Xue1

1 Department of Chemistry, University of Tennessee, Knoxville, TN 37996, USA
2 Chemical and Analytical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
3 Surface Modification and Characterization (SMAC) Research Center, Oak Ridge National Laboratory, Oak Ridge, TN 37831, USA
4 Department of Chemistry, Hong Kong University of Science and Technology, Hong Kong, China
5 Department of Chemistry & Biochemistry, University of Delaware, Newark, DE 19716, USA

Abstract: Reactions of silanes with d0 Ta alkylidene and Group 4 amide complexes were found to involve the initial attack on silicon atoms in the silanes by nucleophilic alkylidene carbon or amide nitrogen atoms. The reaction of (Me3SiCH2) 3Ta (PMe 3) [=CHSiMe3] (1) with H2SiR'Ph (R' = Me, Ph) gave (Me3SiCH2) 3Ta[=C (SiMe 3) SiHR'Ph] (2a-b). Similar reactions of these two silanes and (H2PhSi) 2CH2 with (Me3SiCH2) Ta (PMe3) 2[=CHR]2 (R = SiMe3, 3; CMe3, 4) yielded novel metallasilacyclobutadienes and a metalladisilacyclohexadiene, respectively. In comparison, the reactions between M (NMe2) 4 (M = Ti, Zr, Hf) and silanes were found to give aminosilanes and metal amide hydride species which were perhaps involved in the formation of titanium-silicon-nitride (Ti-Si-N) ternary materials.