Zwitterionic Heavier Pnictinidenes in Redox Catalysis
Abstract
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.
Article Details
Authors (8)
Selwin Fernando
Department of Chemistry Imperial College London Molecular Sciences Research Hub London UK
Yi Chen Chan
Department of Chemistry, Molecular Sciences Research Hub Imperial College London 82 Wood Lane, Shepherds Bush London W12 0BZ UK
Sergio Fernandez
Department of Chemistry Imperial College London Molecular Sciences Research Hub London UK
Enric Sabater
General and Inorganic Chemistry Department University of Saarland Campus C4.1 66123 Saarbrücken Germany
Graham Tizzard
EPSRC National Crystallography Service, School of Chemistry and Chemical Engineering University of Southampton Southampton SO17 1BJ UK
Simon J. Coles
National Crystallography Service
Diego M. Andrada
General and Inorganic Chemistry Department, University of Saarland, Campus C4.1, Saarbrücken 66123, Germany
Oriol Planas
Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, Shepherds Bush, London W12 0BZ, U.K.