[η(5):σ-二甲基碳(C5H4)(C2B10H10)]钛(R)(NMe2)的合成、结构表征、反应活性及热稳定性

Synthesis, structural characterization, reactivity, and thermal stability of [eta(5):sigma-Me2C(C5H4)(C2B10H10)]Ti(R)(NMe2).

作者信息

Wang Hong, Wang Yaorong, Chan Hoi-Shan, Xie Zuowei

机构信息

Department of Chemistry and Center of Novel Functional Molecules, Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China.

出版信息

Inorg Chem. 2006 Jul 10;45(14):5675-83. doi: 10.1021/ic0604664.

DOI:10.1021/ic0604664

PMID:16813433

Abstract

Reaction of [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]TiCl(NMe2) (1) with 1 equiv of PhCH2K, MeMgBr, or Me3SiCH2Li gave corresponding organotitanium alkyl complexes [eta:(5)sigma-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 {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe)(mu:sigma-CH2NMe) (3). Complex 5 slowly decomposed to generate a mixed-valence dinuclear species {[eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti}2(mu-NMe2)(mu:sigma-CH2NMe) (6). Complex 1 reacted with 1 equiv of PhNCO or 2,6-Me2C6H3NC to afford the corresponding monoinsertion product [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-OC(NMe2)NPh] (7) or [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(Cl)[eta(2)-C(NMe2)=N(2,6-Me2C6H3)] (8). Reaction of 4 or 5 with 1 equiv of R'NC gave the titanium eta(2)-iminoacyl complexes [eta:(5)sigma-Me2C(C5H4)(C2B10H10)]Ti(NMe2)[eta(2)-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.

摘要

[η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]TiCl(NMe₂) (1) 与 1 当量的 PhCH₂K、MeMgBr 或 Me₃SiCH₂Li 反应，以良好的产率得到相应的有机钛烷基配合物 [η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti(R)(NMe₂) (R = CH₂Ph (2)、CH₂SiMe₃ (4) 或 Me (5))。用 1 当量的 n-BuLi 处理 1 得到分解产物 {[η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti}₂(μ-NMe)(μ:σ-CH₂NMe) (3)。配合物 5 缓慢分解生成混合价双核物种 {[η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti}₂(μ-NMe₂)(μ:σ-CH₂NMe) (6)。配合物 1 与 1 当量的 PhNCO 或 2,6-Me₂C₆H₃NC 反应，得到相应的单插入产物 [η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti(Cl)[η²-OC(NMe₂)NPh] (7) 或 [η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti(Cl)[η²-C(NMe₂)=N(2,6-Me₂C₆H₃)] (8)。4 或 5 与 1 当量的 R'NC 反应得到钛 η²-亚氨基酰基配合物 [η⁵σ-Me₂C(C₅H₄)(C₂B₁₀H₁₀)]Ti(NMe₂)[η²-C(R)=N(R')] (R = CH₂SiMe₃, R' = 2,6-Me₂C₆H₃ (9) 或 tBu (10); R = Me, R' = 2,6-Me₂C₆H₃ (11) 或 tBu (12))。结果表明，不饱和分子仅在不存在 Ti-C(烷基)键的情况下插入 Ti-N 键中，且 Ti-C(笼)键保持完整。所有配合物均通过各种光谱技术和元素分析进行了全面表征。2、3、6 - 8 和 10 - 12 的分子结构通过单晶 X 射线分析进一步得到证实。