Synthesis, Structural Characterization, Reactivity, and Thermal Stability of [η<sup>5</sup>:<i>σ</i>-Me<sub>2</sub>C(C<sub>5</sub>H<sub>4</sub>)(C<sub>2</sub>B<sub>10</sub>H<sub>10</sub>)]Ti(R)(NMe<sub>2</sub>)
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Reaction of [η:5σ-Me2C(C5H4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [η:5σ-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:5σ-Me2C(C5H4)(C2B10H10)]Ti}2(μ-NMe)(μ:σ-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[η:5σ-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:5σ-Me2C(C5H4)(C2B10H10)]Ti(Cl)[η2-OC(NMe2)NPh] (7) or [η:5σ-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 η2-iminoacyl complexes [η:5σ-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[η2-C(R)N(R‘)] (R = CH2SiMe3, R‘ = 2,6-Me2C6H3 (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.
