Five-Coordinate Platinum(IV) Complex as a Precursor to a Novel Pt(II) Olefin Hydride Complex for Alkane Activation

The five-coordinate platinum(IV) complex (nacnac)PtMe₃ (nacnac^- = [{(o-ⁱPr₂C₆H₃)NC(CH₃)}₂CH]^-) thermally eliminates ethane and methane to produce a novel olefin(hydrido)platinum(II) complex, where the olefin is part of the nacnac-type ligand. This Pt(II) product activates hydrocarbons, including alkanes under mild conditions, as indicated by scrambling of hydrogen and deuterium between the hydrocarbon solvent and selected positions on the ligand of the platinum complex. A mechanism in which olefin insertion into the metal hydride bond opens a site to allow hydrocarbon coordination and C−H bond oxidative addition is proposed.