PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

The reactivity of a series of oxidants with [(tbpy)Pt(Ph)(L)]+ and [(tbpy)2Rh(Me)(OTf)]+ [tbpy = 4,4′-di-tert-butyl-2,2′-bipyridine, L = thf or triflate (OTf)] complexes was investigated. The PtII and RhIII complexes [(tbpy)Pt(Ph)(ONMe3)][BAr′4], [(tbpy)Pt(Ph)(OPy)][BAr′4], [(tbpy)2Rh(Me)(ONMe3)][BAr′4][OTf], and [(tbpy)2Rh(Me)(OPy)][BAr′4][OTF] (Ar′ = 3,5-(CF3)2C6H3, OPy = pyridine N-oxide) have been isolated and characterized by 1H, 13C, and 19F NMR spectroscopy as well as elemental analysis. In addition, single-crystal X-ray diffraction studies of the complexes [(tbpy)Pt(Ph)(OPy)][BAr′4], [(tbpy)2Rh(Cl)2][BAr′4], [(tbpy)2Rh(Me)2][BAr′4], [(tbpy)2Rh(Me)(I)][BAr′4], and [(tbpy)2Rh(Me)(OPy)][BAr′4][OTf] are reported. DFT calculations computationally model the conversions of Pt–Ph and Rh–Me species to the corresponding Pt–OPh and Rh–OMe complexes, providing insight into activation barriers for the oxygen-atom insertion into PtII–R and RhIII–R bonds.