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

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

Journal

Mendeleev Communications
ISSN: 1364-551X , E-ISSN: 0959-9436

Output data

Year: 2025, Volume: 35, Number: 6, Pages: 708-710 Pages count : 3 DOI: 10.71267/mencom.7818

Authors

Pospelov Evgeny V. ¹ , Golovanov Ivan S. ¹ , Sukhorukov Alexey Yu ¹ , Chen Jianzhong ² , Zhang Wanbin ² , Gridnev Ilya Dmitrievich ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russian Federation
2	School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240 Shanghai, P. R. China

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.

Pospelov E.V. , Golovanov I.S. , Sukhorukov A.Y. , Chen J. , Zhang W. , Gridnev I.D.
Mechanism of formation of active catalytic species in nickel-catalysed asymmetric hydrogenation
Mendeleev Communications. 2025. V.35. N6. P.708-710. DOI: 10.71267/mencom.7818 WOS Scopus OpenAlex

Web of science:	WOS:001629936900005
Scopus:	2-s2.0-105021377668
OpenAlex:	W4415383257

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