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A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts

Experimental and computational studies address key questions in a structure–function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN(2)S(2) or [(NO)Fe]N(2)S(2) as donors to (η(5)-C(5)H(5))Fe(CO)(+) or [Fe(NO)(2)](+/0) generate a series of four bimetallics, gradually “soften...

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Autores principales: Ghosh, Pokhraj, Ding, Shengda, Chupik, Rachel B., Quiroz, Manuel, Hsieh, Chung-Hung, Bhuvanesh, Nattami, Hall, Michael B., Darensbourg, Marcetta Y.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Royal Society of Chemistry 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5858031/
https://www.ncbi.nlm.nih.gov/pubmed/29619175
http://dx.doi.org/10.1039/c7sc03378h
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author Ghosh, Pokhraj
Ding, Shengda
Chupik, Rachel B.
Quiroz, Manuel
Hsieh, Chung-Hung
Bhuvanesh, Nattami
Hall, Michael B.
Darensbourg, Marcetta Y.
author_facet Ghosh, Pokhraj
Ding, Shengda
Chupik, Rachel B.
Quiroz, Manuel
Hsieh, Chung-Hung
Bhuvanesh, Nattami
Hall, Michael B.
Darensbourg, Marcetta Y.
author_sort Ghosh, Pokhraj
collection PubMed
description Experimental and computational studies address key questions in a structure–function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN(2)S(2) or [(NO)Fe]N(2)S(2) as donors to (η(5)-C(5)H(5))Fe(CO)(+) or [Fe(NO)(2)](+/0) generate a series of four bimetallics, gradually “softened” by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox levels, demonstrating required features of electrocatalysis. Computational modeling of experimental structures and likely transient intermediates that connect the electrochemical events find roles for electron delocalization by NO, as well as Fe–S bond dissociation that produce a terminal thiolate as pendant base well positioned to facilitate proton uptake and transfer. Dihydrogen formation is via proton/hydride coupling by internal S–H(+)···(–)H–Fe units of the “harder” bimetallic arrangements with more localized electron density, while softer units convert H(–)···H(–)via reductive elimination from two Fe–H deriving from the highly delocalized, doubly reduced [Fe(2)(NO)(3)](–) derivative. Computational studies also account for the inactivity of a Ni(2)Fe complex resulting from entanglement of added H(+) in a pinched –S(δ–)···H(+)···(δ–)S– arrangement.
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spelling pubmed-58580312018-04-04 A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts Ghosh, Pokhraj Ding, Shengda Chupik, Rachel B. Quiroz, Manuel Hsieh, Chung-Hung Bhuvanesh, Nattami Hall, Michael B. Darensbourg, Marcetta Y. Chem Sci Chemistry Experimental and computational studies address key questions in a structure–function analysis of bioinspired electrocatalysts for the HER. Combinations of NiN(2)S(2) or [(NO)Fe]N(2)S(2) as donors to (η(5)-C(5)H(5))Fe(CO)(+) or [Fe(NO)(2)](+/0) generate a series of four bimetallics, gradually “softened” by increasing nitrosylation, from 0 to 3, by the non-innocent NO ligands. The nitrosylated NiFe complexes are isolated and structurally characterized in two redox levels, demonstrating required features of electrocatalysis. Computational modeling of experimental structures and likely transient intermediates that connect the electrochemical events find roles for electron delocalization by NO, as well as Fe–S bond dissociation that produce a terminal thiolate as pendant base well positioned to facilitate proton uptake and transfer. Dihydrogen formation is via proton/hydride coupling by internal S–H(+)···(–)H–Fe units of the “harder” bimetallic arrangements with more localized electron density, while softer units convert H(–)···H(–)via reductive elimination from two Fe–H deriving from the highly delocalized, doubly reduced [Fe(2)(NO)(3)](–) derivative. Computational studies also account for the inactivity of a Ni(2)Fe complex resulting from entanglement of added H(+) in a pinched –S(δ–)···H(+)···(δ–)S– arrangement. Royal Society of Chemistry 2017-12-01 2017-10-12 /pmc/articles/PMC5858031/ /pubmed/29619175 http://dx.doi.org/10.1039/c7sc03378h Text en This journal is © The Royal Society of Chemistry 2017 http://creativecommons.org/licenses/by/3.0/ This article is freely available. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)
spellingShingle Chemistry
Ghosh, Pokhraj
Ding, Shengda
Chupik, Rachel B.
Quiroz, Manuel
Hsieh, Chung-Hung
Bhuvanesh, Nattami
Hall, Michael B.
Darensbourg, Marcetta Y.
A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title_full A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title_fullStr A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title_full_unstemmed A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title_short A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
title_sort matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5858031/
https://www.ncbi.nlm.nih.gov/pubmed/29619175
http://dx.doi.org/10.1039/c7sc03378h
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