Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates
Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates
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DOI：
10.1039/c3sc50462j
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发表时间：
2013-01-01
期刊：
影响因子：
8.4
通讯作者：
Nocera, Daniel G.
中科院分区：
文献类型：
--
作者：
Powers, David C.;Chambers, Matthew B.;Nocera, Daniel G.
卤素的光消除是HX裂解光催化的关键步骤。在这里，我们报道了一对价同分异构体磷氮烷配合物的光还原，并认为在混合价和价对称的配合物的光化学中都有一个共同的中间体。这些研究的结果表明，卤素的光消除通过两个顺序的光化学反应进行：配体解离，随后的卤素消除。
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.