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 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.