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

Dalton Transactions : an International Journal of Inorganic Chemistry
Cheng HouZhuofeng Ke

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 fie...Continue Reading

References

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Citations

May 25, 2016·Journal of the American Chemical Society·Saravanakumar ElangovanMatthias Beller
Apr 7, 2017·Chemistry : a European Journal·Pim PuylaertJohannes G de Vries
Apr 3, 2019·Chemistry : a European Journal·Wei ZhouMatthias Beller
Oct 17, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Animesh ChowdhuryPranab Sarkar
May 1, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Chao DuCunyuan Zhao

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