A series of cis-alkynyl­(silyl)­platinum­(II) complexes was prepared via the chemoselective C­(sp)–Si bond cleavage of alkynylsilanes by a platinum(0) complex ligated with the P–N hemilabile bidentate ligand. The coordination of the triple bond to the platinum center triggers selective C­(sp)–Si bond cleavage. Hammett plots of the 31P­{1H} NMR spectroscopic properties (δ and J values) reflect an electronic effect on platinum­(II) complexes; trans substituents of arylethynyl groups are influenced, but cis-positioned silyl groups are not affected, as evidenced by 29Si­{1H} NMR. In comparison, Hammett plots show that C­(sp)–Si bond cleavage rates are accelerated by electron-rich alkynylsilanes, which is opposite to the ordinary oxidative addition of aryl halides to transition metals often observed in catalytic cross-coupling reactions. A DFT calculation reveals that intermediates and transition states are stabilized by electron-rich alkynylsilanes and that the five-membered hemilabile P–N ligand is essential, in which a reactive electron-deficient 14-electron platinum(0) species is produced via the dissociation of nitrogen, giving rise to a monodentate phosphine coordination. Electron-rich alkynylsilanes allow decreased π back-donation from the platinum center to the ligand, accelerating the dissociation of the more labile nitrogen. Steric congestion between diisopropylphosphino and silyl groups thermodynamically disfavors C­(sp)–Si bond cleavage.

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