NDLI: Unusual non-bifunctional mechanism for Co-PNP complex catalyzed transfer hydrogenation governed by the electronic configuration of metal center

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Li, Yinwu Hou, Cheng Zhang, Zhihan Zhao, Cunyuan Ke, Zhuofeng Jiang, Jingxing
Description	Author Affiliation: Hou C ( MOE Key Laboratory of Bioinorganic and Synthetic Chemistry/KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, P. R. China. ceszhcy@mail.sysu.edu.cn kezhf3@mail.sysu.edu.cn.)
Abstract	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 ∼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.
ISSN	14779226
Issue Number	37
Volume Number	44
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-10-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Cobalt Chemistry Coordination Complexes Catalysis Hydrogenation Molecular Conformation Quantum Theory Thermodynamics Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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