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Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture

The nucleophilic properties of cobalt salen complexes are examined using density functional theory to investigate its carbon fixing capacity. In particular, carbon dioxide attack on neutral and anionic cobalt salen molecules is considered. Carbon fixation occurs for the anionic cobalt salen complex...

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Detalles Bibliográficos
Autores principales: Chiong, Meliton R., Paraan, Francis N. C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9067277/
https://www.ncbi.nlm.nih.gov/pubmed/35514489
http://dx.doi.org/10.1039/c9ra01990a
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author Chiong, Meliton R.
Paraan, Francis N. C.
author_facet Chiong, Meliton R.
Paraan, Francis N. C.
author_sort Chiong, Meliton R.
collection PubMed
description The nucleophilic properties of cobalt salen complexes are examined using density functional theory to investigate its carbon fixing capacity. In particular, carbon dioxide attack on neutral and anionic cobalt salen molecules is considered. Carbon fixation occurs for the anionic cobalt salen complex and is due to the nucleophilic interaction between the cobalt center and carbon dioxide molecule in a Co d(z(2))–CO(2) π* interaction. A minimum energy path search by a nudged elastic band calculation reveals a lower forward activation energy for the anionic complex than the neutral complex, indicating that the formation of the anionic complex is thermodynamically and kinetically favored. In this case, the CO(2) molecule is chemisorbed as partial charge transfer from the cobalt center to carbon dioxide is observed. Proposed reaction mechanisms explain how the Co–C bond energy of the CO(2)–cobalt salen complex can be tuned by appropriate substitutions of electron donating or withdrawing groups on the phenyl ring.
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spelling pubmed-90672772022-05-04 Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture Chiong, Meliton R. Paraan, Francis N. C. RSC Adv Chemistry The nucleophilic properties of cobalt salen complexes are examined using density functional theory to investigate its carbon fixing capacity. In particular, carbon dioxide attack on neutral and anionic cobalt salen molecules is considered. Carbon fixation occurs for the anionic cobalt salen complex and is due to the nucleophilic interaction between the cobalt center and carbon dioxide molecule in a Co d(z(2))–CO(2) π* interaction. A minimum energy path search by a nudged elastic band calculation reveals a lower forward activation energy for the anionic complex than the neutral complex, indicating that the formation of the anionic complex is thermodynamically and kinetically favored. In this case, the CO(2) molecule is chemisorbed as partial charge transfer from the cobalt center to carbon dioxide is observed. Proposed reaction mechanisms explain how the Co–C bond energy of the CO(2)–cobalt salen complex can be tuned by appropriate substitutions of electron donating or withdrawing groups on the phenyl ring. The Royal Society of Chemistry 2019-07-26 /pmc/articles/PMC9067277/ /pubmed/35514489 http://dx.doi.org/10.1039/c9ra01990a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Chiong, Meliton R.
Paraan, Francis N. C.
Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title_full Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title_fullStr Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title_full_unstemmed Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title_short Controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
title_sort controlling the nucleophilic properties of cobalt salen complexes for carbon dioxide capture
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9067277/
https://www.ncbi.nlm.nih.gov/pubmed/35514489
http://dx.doi.org/10.1039/c9ra01990a
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