Halogen Photoelimination from Dirhodium Phosphazane Complexes via Chloride-Bridged Intermediates.
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Halogen photoelimination is a critical step in HX-splitting photocatalysis. Herein, we report the photoreduction 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. The results of these investigations suggest that halogen photoelimination proceeds by two sequential photochemical reactions: ligand dissociation followed by subsequent halogen elimination.