Synthesis of Titanium Cyclynes Cp2Ti(OBET) and Cp*2Ti(OBET) and the Unusual Stability of the Bimetallic Complex Ni[Cp2Ti(OBET)] to CO and O2
Synthesis of Titanium Cyclynes Cp2Ti(OBET) and Cp*2Ti(OBET) and the Unusual Stability of the Bimetallic Complex Ni[Cp2Ti(OBET)] to CO and O2
复制标题
钛旋环Cp2Ti(OBET)和Cp*2Ti(OBET)的合成及双金属配合物Ni[Cp2Ti(OBET)]对CO和O2的异常稳定性
DOI：
10.1021/ja9734105
复制
发表时间：
1998
影响因子：
15
通讯作者：
W. Youngs
中科院分区：
文献类型：
--
作者：
Daming Zhang;David B. McConville;Joseph M. Hrabusa;C. Tessier;W. Youngs
二茂钛乙基配合物1因其三阶非线性光学性质，2制备非常硬且热稳定的金属碳化物，3制备双金属镊子配合物而引起了相当大的关注。研究镊子配合物的目的是了解金属-配体相互作用、金属-金属相互作用以及催化活化分子底物中的金属-金属协同作用。最近对乙酰化钛镊子配合物的兴趣，加上我们成功地制备了铂5和14族元素6的配体o-双（乙基）甲苯（OBET，见eq 1）及其金属配合物，促使我们制备了第一个环乙酰化钛配合物：Cp2-Ti (OBET), Cp* 2Ti （OBET）和双金属配合物Ni [Cp2-Ti （OBET)]（Cp）环戊二烯基）。镍衍生物对CO和O2表现出非常惊人的缺乏反应性，特别是与类似的14族化合物Ni [R2E （OBET))](E) Si和Ge）相比。
Titanocene acetylide complexes1 have drawn considerable attention in regards to their third-order nonlinear optical properties, 2 the preparation of very hard and thermally stable metal carbides, 3 and the preparation of bimetallic tweezer complexes. 4 Tweezer complexes have been studied with the goal of understanding metal-ligand interactions, metal-metal interactions, and metal-metal cooperation in catalytically activated molecular substrates. The recent interest in titanium acetylide tweezer complexes coupled with our success in preparing platinum5 and group 14 element6 derivatives of the ligand o-bis (ethynyl) tolane (OBET, see eq 1) and their metal complexes have stimulated us to prepare the first titanium complexes of a cyclic acetylide: Cp2-Ti (OBET), Cp* 2Ti (OBET), and the bimetallic complex Ni [Cp2-Ti (OBET)](Cp) cyclopentadienyl). The nickel derivative shows a very surprising lack of reactivity toward CO and O2, especially when compared to similar group 14 compounds Ni [R2E (OBET))](E) Si and Ge).