Oxidative Addition of MeI to a Rollover Complex of Platinum(II): Isolation of the Kinetic Product

A pair of new Pt­(II)/Pt­(IV) 2,2′-bipyridine cyclometalated rollover complexes have been synthesized and characterized. [Pt­(bpy-H)­(CH₃)­(PMe₃)] (<b>1</b>), where bpy-H = κ²<i>N</i>,<i>C</i>-2,2′-bipyridine, was obtained from the electron-rich precursor <i>cis</i>-[Pt­(CH₃)₂(DMSO)₂] with a one-pot, two step synthesis; its reactivity has been tested with CH₃I, giving the corresponding Pt­(IV) complex <i>cis</i>-[Pt­(bpy-H)­(CH₃)₂(I)­(PMe₃)] (<b>2</b>), which was fully characterized. Crystals suitable for X-ray analysis were obtained and allowed the determination of the structure of isomer <b>2A</b> which is the product of the <i>trans</i> addition of CH₃I, usually thought of as the <i>kinetic</i> product