Low-load Θ-metallacarboranes as safe and efficient photoredox catalysts for UVA-driven oxidation in water
Year: 2025
Type: article
Abstract: Transition metal (TM) ions 4d 6 or 5d 6 configurations, typically used in photoredox catalysis, are often rare and expensive. In contrast, abundant first-row TM ions tend to favor metal-centered excited states, limiting their practical photocatalytic use. Here, we present two efficient 3d 6 and 3d 5 photoredox catalysts, [3,3′-Co(1,2-C 2 B 9 H 11 ) 2 ] − and [3,3′-Fe(1,2-C 2 B 9 H 11 ) 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, 3d 5 or 3d 6 systems can match or outperform heavier TM analogs 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.
Source: Cell Reports Physical Science
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $5,620
Funders: Universitat de Girona, Ministerio de Ciencia, Innovación y Universidades, Generalitat de Catalunya, Departament d'Innovació, Universitats i Empresa, Generalitat de Catalunya, Generalitat Valenciana, Ministerio de Ciencia e Innovación, European Regional Development Fund, Agencia Estatal de Investigación, Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital, Generalitat Valenciana, European Social Fund
Awards: G1102272714, G1175115578, G1288124756, G1422035950, G1572338302, G2064873908, G2262748287, G2792671303, G294895050, G3005324705, G300979063, G3480869486, G38382560, G410571670, G425668148, G451917667, G5080475149, G5145665551, G523076202, G5416773276, G5539308778, G5812639362, G5926798592, G5967599077, G6033112984, G7084143925, G7398047371, G7792291981, G7825598894, G787121397, G8219391472, G8356803275, G87761830, G9000256078
OpenAlex ID: W4414104561