Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties

The synthesis and electrochemical properties of tetranuclear[Fe2S2]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II)complexes have been studied. To this end, a new tetranuclear [Fe2S2] complexcontaining a 5,5′- diisocyanide-2,2′-bipyridine bridging ligand has been designedand coordina...

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Autores: Torres Ruiz, Alejandro, Collado Martínez, Alba, Gómez Gallego, María Del Mar, Ramírez de Arellano, Carmen, Sierra Rodríguez, Miguel Ángel
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/108015
Acceso en línea:https://hdl.handle.net/20.500.14352/108015
Access Level:acceso abierto
Palabra clave:547
Química orgánica (Química)
2306 Química Orgánica
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oai_identifier_str oai:docta.ucm.es:20.500.14352/108015
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spelling Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical propertiesTorres Ruiz, AlejandroCollado Martínez, AlbaGómez Gallego, María Del MarRamírez de Arellano, CarmenSierra Rodríguez, Miguel Ángel547Química orgánica (Química)2306 Química OrgánicaThe synthesis and electrochemical properties of tetranuclear[Fe2S2]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II)complexes have been studied. To this end, a new tetranuclear [Fe2S2] complexcontaining a 5,5′- diisocyanide-2,2′-bipyridine bridging ligand has been designedand coordinated to the metal complexes through the bipyridine moiety. Thus, thetetranuclear [Fe2S2] complex (6) coordinates to Pt(II), Ni(II) and Ru(II) yieldingthe corresponding metal complexes. The new metal center in the bipyridine linkermodulates the electronic communication between the redox-active [Fe2S2] units. Thus, electrochemical studies and DFT calculations have shown that the presenceof metal complexes in the structure strongly affect the electronic communicationbetween the [Fe2S2] centers. In the case of diphosphine platinum compounds 10,the structure of the phosphine ligand plays a crucial role to facilitate or to hinderthe electronic communication between [Fe2S2] moieties. Compound 10a, bearing a dppe ligand, shows weak electroniccommunication (ΔE = 170 mV), whereas the interaction is much weaker in the Pt-dppp derivative 10b (ΔE = 80 mV) and virtuallynegligible in the Pt-dppf complex 10c. The electronic communication is facilitated by incorporation of a Ru-bis(bipyridine) complex,as observed in the BF4 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 theredox-active centers, which, in turn, can be modulated by a transition metal.ACSUniversidad Complutense de Madrid20232023-01-0120232023-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://hdl.handle.net/20.500.14352/108015reponame:Docta Complutenseinstname:Universidad Complutense de Madrid (UCM)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:docta.ucm.es:20.500.14352/1080152026-06-02T12:44:21Z
dc.title.none.fl_str_mv Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties
title Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties
spellingShingle Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties
Torres Ruiz, Alejandro
547
Química orgánica (Química)
2306 Química Orgánica
title_short 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_sort Heteropolymetallic [FeFe]-hydrogenase mimics: synthesis and electrochemical properties
dc.creator.none.fl_str_mv Torres Ruiz, Alejandro
Collado Martínez, Alba
Gómez Gallego, María Del Mar
Ramírez de Arellano, Carmen
Sierra Rodríguez, Miguel Ángel
author Torres Ruiz, Alejandro
author_facet Torres Ruiz, Alejandro
Collado Martínez, Alba
Gómez Gallego, María Del Mar
Ramírez de Arellano, Carmen
Sierra Rodríguez, Miguel Ángel
author_role author
author2 Collado Martínez, Alba
Gómez Gallego, María Del Mar
Ramírez de Arellano, Carmen
Sierra Rodríguez, Miguel Ángel
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Universidad Complutense de Madrid
dc.subject.none.fl_str_mv 547
Química orgánica (Química)
2306 Química Orgánica
topic 547
Química orgánica (Química)
2306 Química Orgánica
description The synthesis and electrochemical properties of tetranuclear[Fe2S2]-hydrogenase mimic species containing Pt(II), Ni(II), and Ru(II)complexes have been studied. To this end, a new tetranuclear [Fe2S2] complexcontaining a 5,5′- diisocyanide-2,2′-bipyridine bridging ligand has been designedand coordinated to the metal complexes through the bipyridine moiety. Thus, thetetranuclear [Fe2S2] complex (6) coordinates to Pt(II), Ni(II) and Ru(II) yieldingthe corresponding metal complexes. The new metal center in the bipyridine linkermodulates the electronic communication between the redox-active [Fe2S2] units. Thus, electrochemical studies and DFT calculations have shown that the presenceof metal complexes in the structure strongly affect the electronic communicationbetween the [Fe2S2] centers. In the case of diphosphine platinum compounds 10,the structure of the phosphine ligand plays a crucial role to facilitate or to hinderthe electronic communication between [Fe2S2] moieties. Compound 10a, bearing a dppe ligand, shows weak electroniccommunication (ΔE = 170 mV), whereas the interaction is much weaker in the Pt-dppp derivative 10b (ΔE = 80 mV) and virtuallynegligible in the Pt-dppf complex 10c. The electronic communication is facilitated by incorporation of a Ru-bis(bipyridine) complex,as observed in the BF4 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 theredox-active centers, which, in turn, can be modulated by a transition metal.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023-01-01
2023
2023-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/20.500.14352/108015
url https://hdl.handle.net/20.500.14352/108015
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv ACS
publisher.none.fl_str_mv ACS
dc.source.none.fl_str_mv reponame:Docta Complutense
instname:Universidad Complutense de Madrid (UCM)
instname_str Universidad Complutense de Madrid (UCM)
reponame_str Docta Complutense
collection Docta Complutense
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,223283

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