Main group elements have recently emerged as promising candidates for redox catalysis, challenging the traditional reliance on tran-sition metals. Despite heavy group 14 elements, such as germanium, possessing variable oxidation states that suggest their redox catalytic potential, their practical applications have been limited. In this study, we present the synthesis of a carbodiphosphoranyl germanium(II) compound and investigate its redox catalytic application. This organogermanium(II) species exhibits excellent catalytic performance in promoting the transfer hydrogenation of azoarenes and imines under mild conditions. Mechanistic studies re-vealed two distinct catalytic platforms based on Ge(II)/Ge(III)/Ge(IV) and Ge(II)/Ge(IV) redox cycles at a single germanium centre. These results enable us to achieve the catalytic hydrogenation of azoarenes mediated by frustrated radical pairs (FRPs), as well as the catalytic chemoselective dearomatization of N-heteroarenes undergoing Ge(II)/Ge(IV) redox process. Our work demonstrates the capacity of main group catalysts to facilitate diverse challenging chemical transformations through regulating the catalytic modes.
This study was published in Journal of the American Chemical Society (https://doi.org/10.1021/jacs.5c12407) entitled “Germanium-Mediated Catalysis via Ge(II)/Ge(III)/Ge(IV) or Ge(II)/Ge(IV) Redox Cycling”. Prof. Zhaowen Dong is the corresponding author of the paper, and Ph.D. student Yihan Zhou, Zhuchunguang Liu and Master’s student Huan Mu are the co-first authors. This work was financially supported by the National Natural Science Foundation of China, National Key R&D Program of China, and Natural Science Foundation of Sichuan, China and the Fundamental Research Funds for the Central Universities.
