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

Pure and Applied Chemistry

Vol. 73, Issue 2

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,

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

* Lecture presented at the XIXth International Conference on Organometallic Chemistry (XIX ICOMC) , Shanghai, China, 23-28 July 2000. Other presentations are published in this issue, pp. 205-376.
** Corresponding author

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