Germanium-Mediated Catalysis via Ge(II)/Ge(III)/Ge(IV) or Ge(II)/Ge(IV) Redox Cycling

作者：YG Zhou, Zhuchunguang Liu, Huan Mu, Hanjiao Chen, Xinran Fu, Bo Xiao, Weichao Xue, Jiliang Zhou, Zhaowen Dong · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c12407 · 被引用次数：15 · 研究领域：Organoboron and organosilicon chemistry、Synthesis and characterization of novel inorganic/organometallic compounds、Organometallic Complex Synthesis and Catalysis

Main group elements have recently emerged as promising candidates for redox catalysis, challenging the traditional reliance on transition 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 revealed two distinct catalytic platforms based on Ge II /Ge III /Ge IV and Ge II /Ge IV redox cycles at a single germanium center. 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 a 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.