Evolution of H2 by simple dissolution of either [Pt2(NH3)4(C4H6NO)2]2-(PF6)4, [Pt4(NH3)8(C4H6NO)4](NO3)2(PF6)3·5H2O or [Pt4(NH3)8(C4H6NO)4]-(NO3) 6·2H2O (C4H6NO is deprotonated α-pyrrolidone) into water, without light irradiation, is observed by gas chromatography. The H2 evolution seems to be due to an interaction between [Pt4(NH3)8(C4H6NO)4]6+ and proton, which is confirmed by UV-visible spectrophotometry. An attempt is made to utilize the reaction in the photochemical reduction of water into hydrogen. [Pt4(NH3)8(C4H6NO)4]6+ and [Pt4(NH3)8(C5H4NO)4]5+ are used as homogeneous hydrogen-producing catalysts in a photochemical model system containing EDTA as sacrificial electron donor, Ru(bpy)32+ as a photosensitizer and methyl-viologen (MV2+) as an electron relay. Quantum yields for their hydrogen productions are calculated to be 0.022 and 0.11, respectively.
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