Abstract
The 2-vinylpyridinate complex [PtMe(Vpy)(DMSO)], C, is successfully prepared from dimeric platinum(II) complex cis,cis-[Me2Pt(μ-SMe2)2PtMe2], B, in the presence of DMSO and 2-vinylpyridine ligand. The DMSO molecule in complex C can be readily substituted by methyldiphenylphosphine (PPh2Me), allowing synthesis of [PtMe(Vpy)(PPh2Me)], 1, which has been fully characterized spectroscopically. Complex 1 is emissive in solid state and solution at room temperature and at 77 K. This complex displays an intense phosphorescence emission (with a significantly long lifetime) which is originated from mixed 3ILCT/3MLCT excited state. Additionally, complex 1 undergoes oxidative addition with alkyl halide (MeI) bearing [PtMe2I(Vpy)(PPh2Me)], 2, after 2 h. Kinetic studies suggest that the latter reaction (oxidative addition) proceed by a classical SN2 mechanism. The rate of oxidative addition reaction at different temperatures is measured and high negative ΔS# value is obtained for the reaction which supported the proposed mechanism. On the basis of NMR spectroscopy, when complex 1 reacts with MeI under extended time (5 days), complex 2 gradually converts to a mixture of platinum complexes trans-[PtMeI(PPh2Me)2], 3, [{PtMe2(Vpy)2(μ-I)2], 4, and a free ligand Z/E-[C8H9N], 5, based on the carbon–carbon bond coupling.
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