Reactions of d<sup>0</sup> alkylidene and amide complexes with silanes

Diminnie, Jonathan B.; Liu, Xiaozhan; Cai, Hu; Wu, Zhongzhi; Blanton, Jaime R.; Chen, Tianniu; Tuinman, Albert A.; Quisenberry, Keith T.; Vallet, Catherine E.; Zuhr, Ray A.; Beach, David B.; Peng, Zhihui; Wu, Yun-Dong; Concolino, Thomas E.; Rheingold, Arnold L.; Xue, Ziling

doi:10.1351/pac200173020331

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

http://dx.doi.org/10.1351/pac200173020331

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 (PMe₃) [=CHSiMe₃] (1) with H₂SiR'Ph (R' = Me, Ph) gave (Me₃SiCH₂) ₃Ta[=C (SiMe₃) 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.