Synthesis and Structure of Cp*2TiH, Cp*2TiH2Li(tmed), and [Cp*2TiOLi(THF)]2
Synthesis and Structure of Cp*2TiH, Cp*2TiH2Li(tmed), and [Cp*2TiOLi(THF)]2
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Cp*2TiH、Cp*2TiH2Li(tmed) 和 [Cp*2TiOLi(THF)]2 的合成和结构
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发表时间：
1998
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通讯作者：
R. Andersen
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作者：
W. Lukens;P. Matsunaga;R. Andersen
d1氢化物Cp*2TiH的固态晶体结构表明，它具有一个开放的Cp*（质心）- Ti - Cp*（质心）角为150°的弯曲夹层结构。晶体结构在不对称单元中包含两个分子，通过各向同性热参数定位和细化到每个独立分子中Ti−H距离分别为1.69(5)和1.84(4)a；平均Ti - H距离为1.76 A。在每个分子中，Ti−H向量位于弯曲茂金属的理想C2轴上。正己烷中n- bui和Me2NCH2CH2NMe2 （tmed）加成成Cp*2TiH或[Li(tmed)]2C10H8加成Cp*2TiCl得到阴离子二氢化物Cp*2Ti(μ-H)2Li（tmed）。在x射线衍射实验中没有发现氢化物原子的位置，但电子顺磁共振谱显示了与两个等效氢核的耦合，AHiso = 9.6 g。此外，通过6Li同位素体的制备证实了与7Li的耦合，表明未配对的电子与每个氢化氢都有耦合。
The solid-state crystal structure of the d1 hydride Cp*2TiH shows that it has a bent sandwich structure with an open Cp*(centroid)−Ti−Cp*(centroid) angle of 150°. The crystal structure contains two molecules in the asymmetric unit, and the hydridic hydrogen atom is located and refined with isotropic thermal parameters to a Ti−H distance of 1.69(5) and 1.84(4) A in each independent molecule; the average Ti−H distance is 1.76 A. In each molecule, the Ti−H vector lies on the idealized C2 axis of the bent metallocene. The addition of n-BuLi and Me2NCH2CH2NMe2 (tmed) in hexane to Cp*2TiH or the addition of [Li(tmed)]2C10H8 to Cp*2TiCl gives the anionic dihydride Cp*2Ti(μ-H)2Li(tmed). The hydride atoms are not located in the X-ray diffraction experiment, but electron paramagnetic resonance spectra show coupling to two equivalent hydrogen nuclei, AHiso = 9.6 G. In addition, coupling to 7Li, confirmed by the preparation of the 6Li isotopomer, shows that the unpaired electron couples with each hydridic hydrogen an...