Zwitterionic Heavier Pnictinidenes in Redox Catalysis

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.

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Publication Details

Journal
Angewandte Chemie International Edition
Published
2025-06-18
DOI
https://doi.org/10.1002/anie.202505697
Citations
12
Primary Topic
Synthesis and characterization of novel inorganic/organometallic compounds
Type
article
Field-Weighted Citation Impact
6.45

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article

Zwitterionic Heavier Pnictinidenes in Redox Catalysis

Simon John Coles, Oriol Planas, Diego M. Andrada, Graham J. Tizzard et al.
12 citations
Angewandte Chemie International Edition
Synthesis and characterization of novel inorganic/organometallic compounds
6.45
article

Zwitterionic Heavier Pnictinidenes in Redox Catalysis

Simon John Coles, Oriol Planas, Diego M. Andrada, Graham J. Tizzard, Yi‐Chen Chan, Selwin Fernando, Enric Sabater, Sergio Fernández
article en
12 citations

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.

Angewandte Chemie International EditionVol. 64(34)
Queen Mary University of London (GB), Universitat de Girona (ES), University of Southampton (GB), Imperial College London (GB), Saarland University (DE)
Royal Society, Engineering and Physical Sciences Research Council, European Research Council
Openalex Percentile: Top 3%
Synthesis and characterization of novel inorganic/organometallic compounds
6.45
DOIOpen Access PDFOpenAlex
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Zwitterionic Heavier Pnictinidenes in Redox Catalysis — Simon John Coles, Oriol Planas, et al. · Angewandte Chemie International Edition (2025) | TGRS Research Map | TGRS