[PtSb](VII) 配合物光照下的氯的溶解和固态光还原消除。
Solution and solid-state photoreductive elimination of chlorine by irradiation of a [PtSb](VII) complex.
机构信息
Department of Chemistry, Texas A&M University , College Station, Texas 77843, United States.
出版信息
J Am Chem Soc. 2014 Aug 6;136(31):10866-9. doi: 10.1021/ja5056164. Epub 2014 Jul 22.
In our search for novel main-group-based redox-active platforms for solar fuel production, we have synthesized Cl2Sb(IV)Pt(III)Cl3(o-dppp)2 (2, o-dppp = o-(Ph2P)C6H4)), a complex featuring a highly oxidized PtSb core. This thermally stable complex quickly evolves chlorine upon irradiation with a Xe lamp, leading to [Cl2Sb(IV)Pt(I)Cl(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.
在寻找用于太阳能燃料生产的新型主族氧化还原活性平台的过程中，我们合成了 Cl2Sb(IV)Pt(III)Cl3(o-dppp)2（2，o-dppp = o-(Ph2P)C6H4)），这是一种具有高度氧化的PtSb核的配合物。这种热稳定的配合物在 Xe 灯照射下迅速释放出氯气，导致 [Cl2Sb(IV)Pt(I)Cl(o-dppp)2]（1）作为光产物。这种光还原非常有效，当在 CH2Cl2 中浓度为 4.4 M 的 2,3-二甲基-1,3-丁二烯溶液中进行时，最大量子产率为 13.8%。值得注意的是，在没有捕获剂的情况下，2 在固态下也会在环境条件下辐照释放氯气。
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