Reactions of Tantalum Alkylidene Complexes with Silanes. Synthesis and Characterization of Novel Metallasilacyclodiene Complexes and Kinetic and Mechanistic Studies of Their Formation
作者:Jonathan B. Diminnie、Jaime R. Blanton、Hu Cai、Keith T. Quisenberry、Ziling Xue
DOI:10.1021/om000476r
日期:2001.4.1
The reactions of tantalum alkylidene complexes (RCH2)3Ta(L)CHR (1) and RCH2Ta(L)2[CHR]2 (3) (R = SiMe3, L = PMe3) with phenylsilanes H2SiR‘Ph (R‘ = Me, Ph) and (PhSiH2)2CH2 were found to produce bis(silyl)-substituted alkylidene complexes (RCH2)3TaCR(SiHR‘Ph) (4) and novel metallasilacyclobutadiene and metalladisilacyclohexadiene complexes. Reaction of the mixed-ligand trimethylsilylmethyl neopentylidene
钽亚烷基络合物(RCH 2)3 Ta(L)CHR(1)和RCH 2 Ta(L)2 [ CHR] 2(3)(R = SiMe 3,L = PMe 3)与苯基硅烷H 2 SiR的反应发现'Ph(R'= Me,Ph)和(PhSiH 2)2 CH 2产生双(甲硅烷基)取代的亚烷基络合物(RCH 2)3 Ta CR(SiHR'Ph)(4)和新型金属硅硅烷基环丁二烯和金属硅二硅烷基环己二烯配合物。混合配体的三甲基甲硅烷基甲基新亚戊基络合物RCH 2 Ta(L)2 [ CHBu t ] 2(6)与H 2 SiMePh的反应也产生了金属硅烷基环丁二烯络合物,但新戊基新亚戊基络合物Bu t CH 2 Ta(L)2的反应[ CHBu t ] 2(2)与H 2 SiMePh产生未鉴定的产物。1 → 4的氘标记和动力学研究被发现与解离机制是一致的。通过X射线晶体学确定新颖的金属环配合物5a,5b,7和8的结构。