We report two air-stable nickel(II) half-sandwich complexes,Cp*Ni(1,2-Cy_(2)PC_(6)H_(4)O)(1) and Cp*Ni(1,2-Ph_(2)PC_(6)H4NH)(2),for cooperative B-H bond activation and their applications in catalytic hydroboration of ...We report two air-stable nickel(II) half-sandwich complexes,Cp*Ni(1,2-Cy_(2)PC_(6)H_(4)O)(1) and Cp*Ni(1,2-Ph_(2)PC_(6)H4NH)(2),for cooperative B-H bond activation and their applications in catalytic hydroboration of unsaturated organic compounds.Both 1 and 2 react with HBpin by adding the B-H bond across the Ni-X bond (X=O or N),giving rise to the 18-electron Ni(II)-H active species,[H1(Bpin)]and[H_(2)(Bpin)].Subtle tuning of the Ni-X pair and the supporting ancillary phosphine have a significant effect on the reactivity and catalytic performance of Cp*Ni(1,2-R_(2)PC_(6)H_(4)X).Unlike[H_(2)(Bpin)],the activation of HBpin in[H1(Bpin)]is reversible,which enables the Ni-O complex to be an effective cooperative catalyst in the hydroboration of N-heteroarenes,and as well as ketones and imines.展开更多
基金the financial support from the National Natural Science Foundation of China (Nos. 22022102 and 22071010)the financial support from China Postdoctoral Science Foundation (No. 2021M700462)。
文摘We report two air-stable nickel(II) half-sandwich complexes,Cp*Ni(1,2-Cy_(2)PC_(6)H_(4)O)(1) and Cp*Ni(1,2-Ph_(2)PC_(6)H4NH)(2),for cooperative B-H bond activation and their applications in catalytic hydroboration of unsaturated organic compounds.Both 1 and 2 react with HBpin by adding the B-H bond across the Ni-X bond (X=O or N),giving rise to the 18-electron Ni(II)-H active species,[H1(Bpin)]and[H_(2)(Bpin)].Subtle tuning of the Ni-X pair and the supporting ancillary phosphine have a significant effect on the reactivity and catalytic performance of Cp*Ni(1,2-R_(2)PC_(6)H_(4)X).Unlike[H_(2)(Bpin)],the activation of HBpin in[H1(Bpin)]is reversible,which enables the Ni-O complex to be an effective cooperative catalyst in the hydroboration of N-heteroarenes,and as well as ketones and imines.
