Zwitterionic Heavier Pnictinidenes in Redox Catalysis

Herein we describe a new class of zwitterionic heavier pnictogen species with bis(NHC)borate as stabilizing ligands, enabling the isolation of Sb and Bi species in +1, +2, and +3 oxidation states. Computational analysis of zwitterionic pnictinidines revealed their cationis character, as well as unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in key organometallic transformations, including oxidative addition and reductive elimination pro-cesses, and display redox catalytic activity in hydrodefluorination reactions, marking a rare example of pnictinidine-catalyzed redox transformation beyond the constraints of pincer ligands. Additionally, we report on a novel dehydrogenative thiolation of silanes. This work expands the scope of low-valent pnictogen chemistry, providing a novel platform for main group redox catalysis.