Photochemically induced reductive elimination of hydrogen from a binuclear platinum hydride

Article abstract of DOI:10.1021/ic00140a012

Photolysis of [Pt₂H₂(μ-H)(μ-dppm)₂] [PF₆] (Ia), dppm = Ph₂PCH₂PPh₂, using 362 ± 8 nm light occurs with quantum yields of 0.81 (MeCN solution) and 0.57 (pyridine solution) to give [Pt₂H(L) (μ-dppm)₂][PF₆] (IIc, L = MeCN; IId, L = pyridine) and H₂ in quantitative yield. The primary isotopic effect on the quantum yields (from similar studies of [Pt₂D₃(μ-dppm)₂][PF₆] (Ib)) is given by φ_H/φ_D = 1.8 and 1.6 in MeCN and pyridine solutions, respectively, and the reductive elimination is shown to be intramolecular (a mixture of Ia and Ib gives very largely H₂ and D₂ with little HD). The reaction can be sensitized with triphenylene but not by Michler's ketone, indicating that reaction is initiated from the singlet excited state.