Tetranuclear rollover cyclometalated organoplatinum–rhenium compounds; C–I oxidative addition and C–C reductive elimination using a rollover cycloplatinated dimer

Abstract

The novel tetranuclear Pt(IV)–Re(VII) complex [Pt₂Me₄(OReO₃)₂(PMePh₂)₂(µ-bpy-2H)], 4, is synthesized through the reaction of silver perrhenate with a new rollover cycloplatinated(IV) complex [Pt₂Me₄I₂(PMePh₂)₂(µ-bpy-2H)], 3. In complex 4, while 2,2′-bipyridine (bpy) acts as a linker between two Pt metal centers, oxygen acts as a mono-bridging atom between Pt and Re centers through an unsupported Pt(IV)–O–Re(VII) bridge. The precursor rollover cycloplatinated(IV) complex 3 is prepared by the MeI oxidative addition reaction of the rollover cycloplatinated(II) complex [Pt₂Me₂(PMePh₂)₂(µ-bpy-2H)], 2. Complex 2 shows a metal-to-ligand charge-transfer band in the visible region, which was used to investigate the kinetics and mechanism of its double MeI oxidative addition reaction. Based on the experimental findings, the classical S_N2 mechanism was suggested for both steps and supported by computational studies. All complexes are fully characterized using multinuclear NMR spectroscopy and elemental analysis. Attempts to grow crystals of the rollover cycloplatinated(IV) dimer 3 yielded a new dimer rollover cyclometalated complex [Pt₂I₂(PMePh₂)₂(µ-bpy-2H)], 5, presumably from the C–C reductive elimination of ethane. The identity of complex 5 was confirmed by single crystal X-ray diffraction analysis.