Zwitterionic heavier pnictinidenes in redox catalysis
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.
Antimony, Bismuth, N-Heterocyclic carbene ligands, Organometallic chemistry, Redox catalysis
Fernando, Selwin
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Chan, Yi Chen
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Fernandez, Sergio
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Sabater, Enric
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Tizzard, Graham
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Coles, Simon J.
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Andrada, Diego M.
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Planas, Oriol
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Fernando, Selwin
e6bc4c9a-c915-45bc-8d14-ce82ea5b398f
Chan, Yi Chen
67dcde79-84b6-4637-af25-21afb2c9efcd
Fernandez, Sergio
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Sabater, Enric
e6b81e93-250d-4bef-be17-a4f67d615f7a
Tizzard, Graham
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Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Andrada, Diego M.
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Planas, Oriol
3373e6bf-fb8f-4c08-9901-d6efad3b7d7e
Fernando, Selwin, Chan, Yi Chen, Fernandez, Sergio, Sabater, Enric, Tizzard, Graham, Coles, Simon J., Andrada, Diego M. and Planas, Oriol
(2025)
Zwitterionic heavier pnictinidenes in redox catalysis.
Angewandte Chemie - International Edition, 64 (34), [e202505697].
(doi:10.1002/anie.202505697).
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.
Text
Angew Chem Int Ed - 2025 - Fernando - Zwitterionic Heavier Pnictinidenes in Redox Catalysis
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e-pub ahead of print date: 18 June 2025
Keywords:
Antimony, Bismuth, N-Heterocyclic carbene ligands, Organometallic chemistry, Redox catalysis
Identifiers
Local EPrints ID: 504324
URI: http://eprints.soton.ac.uk/id/eprint/504324
ISSN: 1433-7851
PURE UUID: 61c6c345-241e-49fa-b4c9-1ec16f35d0f9
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Date deposited: 04 Sep 2025 16:41
Last modified: 05 Sep 2025 01:37
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Contributors
Author:
Selwin Fernando
Author:
Yi Chen Chan
Author:
Sergio Fernandez
Author:
Enric Sabater
Author:
Diego M. Andrada
Author:
Oriol Planas
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