905309-45-7Relevant academic research and scientific papers
Synthesis, structural characterization, reactivity, and thermal stability of [η5:σ-Me2C(C5H4)(C 2B10H10)]Ti(R)(NMe2)
Wang, Hong,Wang, Yaorong,Chan, Hoi-Shan,Xie, Zuowei
, p. 5675 - 5683 (2006)
Reaction of [η:5σ-Me2C(C5H 4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH 2Li gave corresponding organotitanium alkyl complexes [η: 5σ-Me2C(C5H4)(C 2B10H10)]Ti(R)(NMe2) (R = CH 2Ph (2), CH2SiMe3 (4), or Me (5)) in good yields. Treatment of 1 with 1 equiv of n-BuLi afforded the decomposition product {[η:5σ-Me2C(C5H4)(C 2B10H10)]Ti}2(μ-NMe)(μ: σ-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[η:5σ-Me 2C(C5H4)(C2B10H 10)]Ti}2(μ-NMe2)(μ:σ-CH 2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me 2C6H3NC to afford the corresponding monoinsertion product [η:5σ-Me2C(C 5H4)(C2B10H10)]Ti(Cl) [η2-OC(NMe2)NPh] (7) or [η:5σ- Me2C(C5H4)(C2B10H 10)]Ti(Cl)[η2-C(NMe2)=N(2,6-Me 2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R′NC gave the titanium η2-iminoacyl complexes [η: 5σ-Me2C(C5H4)(C 2B10H10)]Ti(NMe2)[η2- C(R)=N(R′)] (R = CH2SiMe3, R′ = 2,6-Me 2C6H3 (9) or tBu (10); R = Me, R′ = 2,6-Me2C6H3 (11) or tBu (12)). The results indicated that the unsaturated molecules inserted into the Ti-N bond only in the absence of the Ti-C(alkyl) bond and that the Ti-C(cage) bond remained intact. All complexes were fully characterized by various spectroscopic techniques and elemental analyses. Molecular structures of 2, 3, 6-8, and 10-12 were further confirmed by single-crystal X-ray analyses.
