Photochemical HX splitting reactions (X = halogen) provide a route for solar-to-fuel energy conversion and halogen photoelimination is a critical step in the process.
Scientists in the US have investigated the photoreduction mechanism of a pair of valence-isomeric dirhodium phosphazane complexes and suggest that a common intermediate is accessed in the photochemistry of both mixed-valent and valence-symmetric complexes.
They conclude that halogen photoelimination proceeds by two sequential photochemical reactions: ligand dissociation followed by subsequent halogen elimination, and they hypothesise that complexes that can directly assume a halide-bridged structure will have the highest quantum efficiencies for energy conversion.
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Halogen Photoelimination from Dirhodium Phosphazane Complexes via Chloride-Bridged Intermediates
David C Powers, Matthew B Chambers, Thomas S Teets, Noémie Elgrishi, Bryce L Anderson and Daniel G Nocera
Chem. Sci., 2013, DOI: 10.1039/C3SC50462J
