A cross-metathesis approach for polymetallic [FeFe]-hydrogenase mimics

A method has been developed for synthesizing [FeFe]-H2ase mimics with diverse structures and properties, employing cross-metathesis of olefins. Vinylmetallocenes (5 and 6) and vinyl half-sandwich complexes (10 and 11) have been used as cross-metathesis partners with [FeFe]-H2ase mimics (4, 8, and 9)...

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Detalles Bibliográficos
Autores: Aguado Rivero, Sergio, García Álvarez, Pablo, Cabeza, Javier A., Casarrubios Palomar, Luis, Sierra Rodríguez, Miguel Ángel
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad Complutense de Madrid (UCM)
Repositorio:Docta Complutense
Idioma:inglés
OAI Identifier:oai:docta.ucm.es:20.500.14352/109223
Acceso en línea:https://hdl.handle.net/20.500.14352/109223
Access Level:acceso abierto
Palabra clave:Química orgánica (Química)
2306 Química Orgánica
Descripción
Sumario:A method has been developed for synthesizing [FeFe]-H2ase mimics with diverse structures and properties, employing cross-metathesis of olefins. Vinylmetallocenes (5 and 6) and vinyl half-sandwich complexes (10 and 11) have been used as cross-metathesis partners with [FeFe]-H2ase mimics (4, 8, and 9) bearing a double bond in the moiety attached to the ADT-bridge nitrogen. Electrochemical studies of these complexes, encompassing metallocene-type (7a–b, 12a–b, and 13a–b) as well as half-sandwich derivatives (12c and 13c–d), have demonstrated that the introduction of a redox unit has a marginal impact on the reduction potential of these [FeFe]-H2ase mimics. The application of this cross-metathesis approach has allowed the synthesis of [FeFe]-H2ase mimics featuring an Ir(III) electrochemical antenna (16–18) as well as systems having an electron-donor-photosensitizer structure (ED-PS) (23). The electrocatalytic properties of these complexes have been elucidated through electrochemical studies.