Cp2 TiX Complexes for Sustainable Catalysis in Single-Electron Steps.
Cp2 TiX Complexes for Sustainable Catalysis in Single-Electron Steps.
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DOI：
10.1002/chem.201705707
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发表时间：
2018-04
期刊：
影响因子：
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通讯作者：
R. Richrath;T. Olyschläger;Sven Hildebrandt;Daniel G. Enny;Godfred D. Fianu;R. Flowers;A. Gansäuer
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作者：
R. Richrath;T. Olyschläger;Sven Hildebrandt;Daniel G. Enny;Godfred D. Fianu;R. Flowers;A. Gansäuer
我们提出了一个组合的电化学，动力学和合成研究与一种新的和容易获得的一类二茂钛催化剂的催化在单电子步骤。通过改变阴离子配体X，实现了由容易获得的Cp 2 TiX 2原位制备的我们的Cp 2 TiX-催化剂的电子性质的定制。在研究的络合物中，Cp 2 TiOMs被证明等于或基本上上级于早期开发的最佳催化剂。测定了与催化有关的动力学和热力学性质。它们允许对有效的氧化加成和还原所需的性质的微妙相互作用的机械理解。因此，我们的研究强调，有效的催化剂不需要精心的共价修饰的配位体。
We present a combined electrochemical, kinetic, and synthetic study with a novel and easily accessible class of titanocene catalysts for catalysis in single-electron steps. The tailoring of the electronic properties of our Cp2 TiX-catalysts that are prepared in situ from readily available Cp2 TiX2 is achieved by varying the anionic ligand X. Of the complexes investigated, Cp2 TiOMs proved to be either equal or substantially superior to the best catalysts developed earlier. The kinetic and thermodynamic properties pertinent to catalysis have been determined. They allow a mechanistic understanding of the subtle interplay of properties required for an efficient oxidative addition and reduction. Therefore, our study highlights that efficient catalysts do not require the elaborate covalent modification of the cyclopentadienyl ligands.