Zwitterionic Heavier Pnictinidenes in Redox Catalysis

Abstract Herein, we describe a new class of zwitterionic heavier pnictogen species with bis ( N ‐heterocyclic carbene)borate as ligands, enabling the isolation of stable Sb and Bi species in multiple oxidation states. Computational analysis of zwitterionic pnictinidenes revealed their cationic character at the metal centre while holding unique electronic properties that contribute to their nucleophilicity and stability. These systems participate in oxidative addition and reductive elimination processes, and display redox catalytic activity in hydrodefluorination reactions, marking a unique example of cationic pnictinidene catalysing a redox transformation and providing reactivity 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.