Solution and Solid-State Photoreductive Elimination of Chlorine by Irradiation of a [PtSb]VII Complex

In our search for novel main-group-based redox-active platforms for solar fuel production, we have synthesized Cl2SbIVPtIIICl3(o-dppp)2 (2, o-dppp = o-(Ph2P)C6H4)), a complex featuring a highly oxidized [PtSb]VII core. This thermally stable complex quickly evolves chlorine upon irradiation with a Xe...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-08, Vol.136 (31), p.10866-10869
Main Authors: Yang, Haifeng, Gabbaï, François P.
Format: Article
Language:English
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Summary:In our search for novel main-group-based redox-active platforms for solar fuel production, we have synthesized Cl2SbIVPtIIICl3(o-dppp)2 (2, o-dppp = o-(Ph2P)C6H4)), a complex featuring a highly oxidized [PtSb]VII core. This thermally stable complex quickly evolves chlorine upon irradiation with a Xe lamp, leading to [Cl2SbIVPtICl(o-dppp)2] (1) as the photo­product. This photo­reduction is very efficient, with a maximum quantum yield of 13.8% when carried out in a 4.4 M solution of 2,3-dimethyl-1,3-butadiene in CH2Cl2. Remarkably, 2 also evolves chlorine when irradiated in the solid state under ambient conditions in the absence of a trap.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja5056164