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Halogen Photoelimination from Dirhodium Phosphazane Complexes via Chloride-Bridged Intermediates.

ABSTRACT: 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.

SUBMITTER: Powers DC

PROVIDER: S-EPMC3819227 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

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Halogen Photoelimination from Dirhodium Phosphazane Complexes via Chloride-Bridged Intermediates.

Powers David C DC Chambers Matthew B MB Teets Thomas S TS Elgrishi Noémie N Anderson Bryce L BL Nocera Daniel G DG

Chemical science 20130701 7

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. ...[more]

PMID: 24224081

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