Low-load Θ-metallacarboranes as safe and efficient photoredox catalysts for UVA-driven oxidation in water
Transition-metal (TM) ions 4d6 or 5d6 configurations, typically used in photoredox catalysis, are often rare and expensive. In contrast, abundant first-row TM ions tend to favour metal-centered excited states, limiting their practical photocatalytic use. Here, we present two efficient 3d6 and 3d5 ph...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:10256/27391 |
| Acceso en línea: | http://hdl.handle.net/10256/27391 |
| Access Level: | acceso abierto |
| Palabra clave: | Catàlisi Química quàntica Catalysis Quantum chemistry Química de l'estat excitat Excited state chemistry |
| Sumario: | Transition-metal (TM) ions 4d6 or 5d6 configurations, typically used in photoredox catalysis, are often rare and expensive. In contrast, abundant first-row TM ions tend to favour metal-centered excited states, limiting their practical photocatalytic use. Here, we present two efficient 3d6 and 3d5 photoredox catalysts, [3,3'-Co(1,2-C2B9H11)2]- and [3,3'-Fe(1,2-C2B9H11)2]-, with identical structures and charges (-1). Despite different electronic configurations, both catalysts deliver comparable performances in alcohol and alkene oxidation in water, even at low catalyst loadings (0.01 mol%). The catalysts are designed to operate in water without additional cosolvents thanks to the surfactant properties of both θ-metallacarboranes. The impact of irradiating wavelength, explored through quantum chemistry, rationalizes their photocatalytic outcomes. Remarkably, 3d5 or 3d6 systems can match or outperform heavier TM analogues when supported by boron-based ligands, though selectivity differences highlight the role of metal electronic structure. UVA irradiation significantly boosts [o-COSAN]⁻ activity, offering new design insights for earth-abundant photoredox catalysts |
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