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Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation

Evgeny V. Pospelov 1
Evgeny V. Pospelov
, 
Ivan S. Golovanov 1
Ivan S. Golovanov
, 
Alexey Yu Sukhorukov 1
Alexey Yu Sukhorukov
, 
Jianzhong Chen 2
Jianzhong Chen
, 
Wanbin Zhang 2
Wanbin Zhang
, 
Ilya Dmitrievich Gridnev 1
Ilya Dmitrievich Gridnev
2 School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240 Shanghai, P. R. China
10.71267/mencom.7818
Published 2025-10-21
Communication , Volume 35, Issue 6, 708-710
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Pospelov E. V. et al. Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation // Mendeleev Communications. 2025. Vol. 35. No. 6. pp. 708-710.
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Pospelov E. V., Golovanov I. S., Sukhorukov A. Yu., Chen J., Zhang W., Gridnev I. D. Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation // Mendeleev Communications. 2025. Vol. 35. No. 6. pp. 708-710.
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TY - JOUR
DO - 10.71267/mencom.7818
UR - https://mendcomm.colab.ws/publications/10.71267/mencom.7818
TI - Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation
T2 - Mendeleev Communications
AU - Pospelov, Evgeny V.
AU - Golovanov, Ivan S.
AU - Sukhorukov, Alexey Yu
AU - Chen, Jianzhong
AU - Zhang, Wanbin
AU - Gridnev, Ilya Dmitrievich
PY - 2025
DA - 2025/10/21
PB - Mendeleev Communications
SP - 708-710
IS - 6
VL - 35
ER -
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@article{2025_Pospelov,
author = {Evgeny V. Pospelov and Ivan S. Golovanov and Alexey Yu Sukhorukov and Jianzhong Chen and Wanbin Zhang and Ilya Dmitrievich Gridnev},
title = {Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation},
journal = {Mendeleev Communications},
year = {2025},
volume = {35},
publisher = {Mendeleev Communications},
month = {Oct},
url = {https://mendcomm.colab.ws/publications/10.71267/mencom.7818},
number = {6},
pages = {708--710},
doi = {10.71267/mencom.7818}
}
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Pospelov, Evgeny V., et al. “Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation.” Mendeleev Communications, vol. 35, no. 6, Oct. 2025, pp. 708-710. https://mendcomm.colab.ws/publications/10.71267/mencom.7818.
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Keywords

asymmetric hydrogenation
catalytic cycles
chiral bisphosphines.
DFT computations
Ni complexes
reaction mechanisms

Abstract

Initial stages of two representative Ni-catalysed asymmetric hydrogenations were investigated computationally featuring the formation of the active catalytic species [R,R-BenzP*NiH]+ from R,R-BenzP*Ni(OAc)2 and [S,S-Ph-BPENiH]+ from S,S-Ph-BPENi(OAc)2. Among several computed pathways the most feasible is dissociation of acetic acid from (ligand)NiH(HOAc) formed by H2 metathesis in the (ligand)Ni(H2)(OAc)2. The rate-limiting step is the initial metathesis of H2 requiring high effective activation barriers of 28.3 and 26.6 kcal mol-1, in accord with high pressures and elevated temperatures essential for the Ni-catalysed hydrogenations.

Funders

Russian Science Foundation
24-43-00011

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