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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