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Heteropolymetallic [FeFe]-Hydrogenase Mimics: Synthesis and Electrochemical Properties
[Image: see text] The synthesis and electrochemical properties of tetranuclear [Fe(2)S(2)]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II) complexes have been studied. To this end, a new tetranuclear [Fe(2)S(2)] complex containing a 5,5′-diisocyanide-2,2′-bipyridine bridging ligand h...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9976291/ https://www.ncbi.nlm.nih.gov/pubmed/36780261 http://dx.doi.org/10.1021/acs.inorgchem.2c03355 |
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author | Torres, Alejandro Collado, Alba Gómez-Gallego, Mar de Arellano, Carmen Ramírez Sierra, Miguel A. |
author_facet | Torres, Alejandro Collado, Alba Gómez-Gallego, Mar de Arellano, Carmen Ramírez Sierra, Miguel A. |
author_sort | Torres, Alejandro |
collection | PubMed |
description | [Image: see text] The synthesis and electrochemical properties of tetranuclear [Fe(2)S(2)]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II) complexes have been studied. To this end, a new tetranuclear [Fe(2)S(2)] complex containing a 5,5′-diisocyanide-2,2′-bipyridine bridging ligand has been designed and coordinated to the metal complexes through the bipyridine moiety. Thus, the tetranuclear [Fe(2)S(2)] complex (6) coordinates to Pt(II), Ni(II) and Ru(II) yielding the corresponding metal complexes. The new metal center in the bipyridine linker modulates the electronic communication between the redox-active [Fe(2)S(2)] units. Thus, electrochemical studies and DFT calculations have shown that the presence of metal complexes in the structure strongly affect the electronic communication between the [Fe(2)S(2)] centers. In the case of diphosphine platinum compounds 10, the structure of the phosphine ligand plays a crucial role to facilitate or to hinder the electronic communication between [Fe(2)S(2)] moieties. Compound 10a, bearing a dppe ligand, shows weak electronic communication (ΔE = 170 mV), whereas the interaction is much weaker in the Pt-dppp derivative 10b (ΔE = 80 mV) and virtually negligible in the Pt-dppf complex 10c. The electronic communication is facilitated by incorporation of a Ru-bis(bipyridine) complex, as observed in the BF(4) salt 12 (ΔE = 210 mV) although the reduction of the [FeFe] centers occurs at more negative potentials. Overall, the experimental–computational procedure used in this work allows us to study the electronic interaction between the redox-active centers, which, in turn, can be modulated by a transition metal. |
format | Online Article Text |
id | pubmed-9976291 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-99762912023-03-02 Heteropolymetallic [FeFe]-Hydrogenase Mimics: Synthesis and Electrochemical Properties Torres, Alejandro Collado, Alba Gómez-Gallego, Mar de Arellano, Carmen Ramírez Sierra, Miguel A. Inorg Chem [Image: see text] The synthesis and electrochemical properties of tetranuclear [Fe(2)S(2)]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II) complexes have been studied. To this end, a new tetranuclear [Fe(2)S(2)] complex containing a 5,5′-diisocyanide-2,2′-bipyridine bridging ligand has been designed and coordinated to the metal complexes through the bipyridine moiety. Thus, the tetranuclear [Fe(2)S(2)] complex (6) coordinates to Pt(II), Ni(II) and Ru(II) yielding the corresponding metal complexes. The new metal center in the bipyridine linker modulates the electronic communication between the redox-active [Fe(2)S(2)] units. Thus, electrochemical studies and DFT calculations have shown that the presence of metal complexes in the structure strongly affect the electronic communication between the [Fe(2)S(2)] centers. In the case of diphosphine platinum compounds 10, the structure of the phosphine ligand plays a crucial role to facilitate or to hinder the electronic communication between [Fe(2)S(2)] moieties. Compound 10a, bearing a dppe ligand, shows weak electronic communication (ΔE = 170 mV), whereas the interaction is much weaker in the Pt-dppp derivative 10b (ΔE = 80 mV) and virtually negligible in the Pt-dppf complex 10c. The electronic communication is facilitated by incorporation of a Ru-bis(bipyridine) complex, as observed in the BF(4) salt 12 (ΔE = 210 mV) although the reduction of the [FeFe] centers occurs at more negative potentials. Overall, the experimental–computational procedure used in this work allows us to study the electronic interaction between the redox-active centers, which, in turn, can be modulated by a transition metal. American Chemical Society 2023-02-13 /pmc/articles/PMC9976291/ /pubmed/36780261 http://dx.doi.org/10.1021/acs.inorgchem.2c03355 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Torres, Alejandro Collado, Alba Gómez-Gallego, Mar de Arellano, Carmen Ramírez Sierra, Miguel A. Heteropolymetallic [FeFe]-Hydrogenase Mimics: Synthesis and Electrochemical Properties |
title | Heteropolymetallic
[FeFe]-Hydrogenase Mimics: Synthesis
and Electrochemical Properties |
title_full | Heteropolymetallic
[FeFe]-Hydrogenase Mimics: Synthesis
and Electrochemical Properties |
title_fullStr | Heteropolymetallic
[FeFe]-Hydrogenase Mimics: Synthesis
and Electrochemical Properties |
title_full_unstemmed | Heteropolymetallic
[FeFe]-Hydrogenase Mimics: Synthesis
and Electrochemical Properties |
title_short | Heteropolymetallic
[FeFe]-Hydrogenase Mimics: Synthesis
and Electrochemical Properties |
title_sort | heteropolymetallic
[fefe]-hydrogenase mimics: synthesis
and electrochemical properties |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9976291/ https://www.ncbi.nlm.nih.gov/pubmed/36780261 http://dx.doi.org/10.1021/acs.inorgchem.2c03355 |
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