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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center
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Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center

机译：金属中心电子构型控制的Co-PNP配合物催化转移加氢的异常非双功能机理

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摘要

The mimic of hydrogenases has unleashed a myriad of bifunctional catalysts, which are widely used in the catalytic hydrogenation of polar multiple bonds. With respect to ancillary ligands, the bifunctional mechanism is generally considered to proceed via the metal-ligand cooperation transition state. Inspired by the interesting study conducted by Hanson et al. (Chem Commun., 2013, 49, 10151), we present a computational study of a distinctive example, where a Co-II-PNP catalyst with an ancillary ligand exhibits efficient transfer hydrogenation through a non-bifunctional mechanism. Both the bifunctional and non-bifunctional mechanisms are discussed. The calculated results, which are based on a full model of the catalyst, suggest that the inner-sphere non-bifunctional mechanism is more favorable (by similar to 11 kcal mol(-1)) than the outer-sphere bifunctional mechanism, which is in agreement with the experimental observations. The origin of this mechanistic preference of the Co-II-PNP catalyst can be attributed to its preference for the square planar geometry. A traditional bifunctional mechanism is less plausible for Co-II-PNP due to the high distortion energy caused by the change in electronic configuration with the varied ligand field. Considering previous studies that focus on the development of ligands more often, this computational study indicates that the catalytic hydrogenation mechanism is controlled not only by the structure of the ligand but also by the electronic configuration of the metal center.
机译：氢化酶的模拟物释放了无数双功能催化剂，广泛用于极性多键的催化加氢。关于辅助配体，通常认为双功能机理是通过金属-配体的协作过渡态进行的。受到Hanson等人进行的有趣研究的启发。 （Chem Commun。，2013，49，10151），我们提供了一个独特示例的计算研究，其中具有辅助配体的Co-II-PNP催化剂通过非双功能机理表现出有效的转移氢化作用。讨论了双功能和非双功能机制。基于催化剂的完整模型的计算结果表明，内球非双功能机理比外球双功能机理更有利（通过类似于11 kcal mol（-1））。与实验观察结果一致。 Co-II-PNP催化剂的这种机械偏好的起源可归因于其对方形平面几何形状的偏好。传统的双功能机制对于Co-II-PNP不太合理，这是因为随着配体场的变化，电子构型的变化会导致高畸变能。考虑到以前的研究更多地关注配体的发展，该计算研究表明，催化氢化机理不仅受配体的结构控制，而且还受金属中心的电子构型控制。

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