In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X‐Ray Absorption Spectroscopy,Chemistry - A European Journal

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In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X‐Ray Absorption Spectroscopy
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-02-25 , DOI: 10.1002/chem.201905479
Karl P. J. Gustafson _{1,

2,

3} , Arnar Guðmundsson ₁ , Éva G. Bajnóczi _{4,

5} , Ning Yuan _{2,

4} , Xiaodong Zou ₂ , Ingmar Persson ₄ , Jan‐E. Bäckvall ₁

Affiliation

The activation process of a known Ru‐catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X‐ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert‐butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1‐phenylethanol a fast‐dynamic equilibrium was observed.

中文翻译：

X射线吸收光谱法测定均相钌外消旋催化剂及其活化中间体的原位结构

使用时间分辨的原位X射线吸收光谱技术已详细研究了一种已知的Ru催化剂二羰基（五苯基环戊二烯基）氯化钌的活化过程。数据提供了参与该过程的物质的键长，以及有关键形成和键断裂的信息。补充叔碳酸钾丁醇盐，催化剂被活化并形成醇盐配合物。催化剂活化通过关键的酰基中间体进行，这导致Ru原子周围的配位环境发生完全的结构变化。发现不同催化剂的活化速率高度依赖于环戊二烯基配体的电子性质。在1-苯基乙醇催化消旋过程中，观察到快速动态平衡。

更新日期：2020-02-25

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