Synthesis, Structural Characterization, Reactivity, and Thermal Stability of [η5:σ-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2)

• Published in: Inorganic chemistry Vol. 45; no. 14; pp. 5675 - 5683
• Main Authors: Wang, Hong, Wang, Yaorong, Chan, Hoi-Shan, Xie, Zuowei
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10.07.2006
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic0604664

Reaction of [η:5 σ-Me2C(C5H4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [η:5 σ-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2) (R = CH2Ph (2), CH2SiMe3 (4), or Me (5)) in good yields. Treatment of 1 with 1 equiv of n-BuLi afforded the decomposition product {[η:5 σ-Me2C(C5H4)(C2B10H10)]Ti}2(μ-NMe)(μ:σ-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[η:5 σ-Me2C(C5H4)(C2B10H10)]Ti}2(μ-NMe2)(μ:σ-CH2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me2C6H3NC to afford the corresponding monoinsertion product [η:5 σ-Me2C(C5H4)(C2B10H10)]Ti(Cl)[η2-OC(NMe2)NPh] (7) or [η:5 σ-Me2C(C5H4)(C2B10H10)]Ti(Cl)[η2-C(NMe2)N(2,6-Me2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R‘NC gave the titanium η 2-iminoacyl complexes [η:5 σ-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[η2-C(R)N(R‘)] (R = CH2SiMe3, R‘ = 2,6-Me2C6H3 (9) or t Bu (10); R = Me, R‘ = 2,6-Me2C6H3 (11) or t Bu (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.