Ligand-to-metal charge transfer (LMCT)
photocatalysis
allows the
activation and synthetic utilization of halides and other heteroatoms
in metal complexes. Many metals are known to undergo LMCT but so far
remain underutilized in the field of catalysis. A screening assay
identifying LMCT activity helped us to expand this catalysis concept
to the application of bismuth LMCT in organic radical coupling reactions.
We demonstrate its application for the generation of two different
radicals (chlorine and carboxyl) in net-oxidative as well as redox-neutral
photochemical reactions. Detailed investigation of the model Giese-type
coupling revealed BiCl4
– and BiCl5
2– as catalytically active bismuth species
under 385 nm irradiation. Combined cyclic voltammetry and UV–vis
studies gave insight into the reactivity of the highly reactive bismuth(II)
catalyst fragment.
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