Powers David C, Chambers Matthew B, Teets Thomas S, Elgrishi Noémie, Anderson Bryce L, Nocera Daniel G
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, U.S.A. ; Department of Chemistry and Chemical Biology, 12 Oxford Street, Cambridge, MA 02138-2902.
Chem Sci. 2013 Jul 1;4(7). doi: 10.1039/C3SC50462J.
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.
卤素光消除是HX裂解光催化中的关键步骤。在此,我们报道了一对价异构二铑磷腈配合物的光还原反应,并表明在混合价态和价对称配合物的光化学过程中都能形成一个共同的中间体。这些研究结果表明,卤素光消除是通过两个连续的光化学反应进行的:配体解离,随后是卤素消除。