Issue 7, 2013
From the journal:

Chemical Science

Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates†

David C. Powers,ab   Matthew B. Chambers,ab   Thomas S. Teets,a   Noémie Elgrishi,a   Bryce L. Andersonab  and  Daniel G. Nocera*ab  

* Corresponding authors

a Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA

b Department of Chemistry and Chemical Biology, 12 Oxford Street, Cambridge, MA 02138-2902, USA
E-mail: dnocera@fas.harvard.edu

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.

Graphical abstract: Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates

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Article information

DOI
https://doi.org/10.1039/C3SC50462J
Article type
Edge Article
Submitted
18 Feb 2013
Accepted
15 Apr 2013
First published
17 Apr 2013

Chem. Sci., 2013,4, 2880-2885

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Halogen photoelimination from dirhodium phosphazane complexes via chloride-bridged intermediates

D. C. Powers, M. B. Chambers, T. S. Teets, N. Elgrishi, B. L. Anderson and D. G. Nocera, Chem. Sci., 2013, 4, 2880 DOI: 10.1039/C3SC50462J

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