P3.2 Mechanistic insights and theoretic modeling of the visible-light-mediated oxalate synthesis from CO2 through a TM-photoredox cascade
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Topic and overall goal:
This work package is devoted to the establishing a photoredox scheme for the photo-mediated oxalate synthesis from carbon dioxide catalyzed by transition metal biscarboxylate complexes. Photoredox catalysis and visible-light excitation provides access to reactive radical species from abundant native functional groups. By modulating the oxidation state of transition metal complexes or by energy transfer-mediated excitation of catalytic intermediates, photocatalysis can open access to the activation of formally inert molecules, e.g., of CO2 for the synthesis of oxalates and related products. The following routes will be under investigation: (i) direct reductive elimination through excitation of bismethoxycarbonyl complexes, (ii) synthesis and characterization of bimetallic bismethoxycarbonyl complexes bearing iridium and ruthenium-based photoredox-active nuclei and, (iii) oxalate synthesis from bismethoxycarbonyl complexes using photoredox-active co-catalysts.