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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...
Autores principales: | , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Royal Society of Chemistry
2017
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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. |
format | Online Article Text |
id | pubmed-5858031 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2017 |
publisher | Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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
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title_full | A matrix of heterobimetallic complexes for interrogation of hydrogen evolution reaction electrocatalysts
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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
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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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