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

摘要

In our search for novel main-group-based redox-active platforms for solar fuel production, we have synthesized Cl_2Sb~Ⅳ Pt~Ⅲ Cl_3(o-dppp)_2 (2, o-dppp = o-(Ph_2P)C_6H_4)), a complex featuring a highly oxidized [PtSb]~Ⅶ core. This thermally stable complex quickly evolves chlorine upon irradiation with a Xe lamp, leading to [Cl_2Sb~Ⅳ Pt~ⅠCl(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 CH_2Cl_2. Remarkably, 2 also evolves chlorine when irradiated in the solid state under ambient conditions in the absence of a trap.