Study on the reactivity of dinuclear platinum (III) complexes

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The number of studies on the reactivity and functionality of dinuclear platinum(III) complexes is limited. In order to elucidate the reactivity of dinuclear Pt(III) complexes, we studied the reaction of 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex with H_2 and hydrogenolysis of pyridine-2-thiol in the presence of 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex as a catalyst. Following results were obtained :(1) When 5-methylpyridinethiolato-bridged dinuclear Pt(III) complex reacted with hydrogen in DMF at 150ーC, the C-S bond cleavage of the bridging ligands occurred to liberate 3-picoline. The amount of the liberated picoline increased with increasing applied hydrogen pressure.(2) The catalytic activity of the 5-methylpyridinethiolatobridged dinuclear Pt(III) complex toward C-S bond cleavage of pyridine-2-thiol was examined. The catalytic activity of the Pt(III) complex is higher than that of the corresponding Pt(II) complex.(3) The catalytic activity of the Pt(III) complex depends on the kinds of axial ligand, and it decreases in the order of Cl > Br > I.(4) ^1H NMR study on the hydrogenolysis of pyridinethiol under D_2 atmosphere revealed the formation of deuterated pyridine and picoline. The mechanism of the catalytic C-S bond cleavage of pyridine-2-thiol was proposed.