Solar energy is the most promising carbon neutral energy source for the future. Splitting of simple molecules like HX (X = Cl, Br) has become an attractive way to convert and store solar energy. Halogen photoelimination from metal centers is the most challenging step in photochemical HX splitting cycles. We have synthesized Pt(IV) chloro complexes  trans �Pt(PEt3)2R(Cl)3 (R = Cl,  aryl and PAH fragments), which eliminate chlorine in the presence of halogen traps when irradiated with uv-vis light. The photo-efficiency of Pt--chloride bond activation increases in the presence of Pt(II) complexes trans �Pt(PEt3)2R(Cl) suggesting the absence of molecular chlorine from reductive elimination of Pt(IV) chloro complexes. Also, we propose that the mechanism of halogen photoelimination from Pt(PEt3)2X3R (X = Cl, Br) (R = aryl, Cl, PAH) complexes is cis elimination via radical abstraction.

Platinum(II) assisted chlorine photoelimination from platinum(IV) chloro complexes

247th National Meeting (2014)

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