1. PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents.
- Author
-
Webb, Joanna R., Figg, Travis M., Otten, Brooke M., Cundari, Thomas R., Gunnoe, T. Brent, and Sabat, Michal
- Subjects
CHEMICAL reactions ,BIPYRIDINE ,SPECTRUM analysis ,NUCLEAR magnetic resonance spectroscopy ,CHEMICAL structure - Abstract
The reactivity of a series of oxidants with [(
t bpy)Pt(Ph)(L)]+ and [(t bpy)2 Rh(Me)(OTf)]+ [t bpy = 4,4′-di- tert-butyl-2,2′-bipyridine, L = thf or triflate (OTf)] complexes was investigated. The PtII and RhIII complexes [(t bpy)Pt(Ph)(ONMe3 )][BAr′4 ], [(t bpy)Pt(Ph)(OPy)][BAr′4 ], [(t bpy)2 Rh(Me)(ONMe3 )][BAr′4 ][OTf], and [(t bpy)2 Rh(Me)(OPy)][BAr′4 ][OTF] (Ar′ = 3,5-(CF3 )2 C6 H3 , OPy = pyridine N-oxide) have been isolated and characterized by1 H,13 C, and19 F NMR spectroscopy as well as elemental analysis. In addition, single-crystal X-ray diffraction studies of the complexes [(t bpy)Pt(Ph)(OPy)][BAr′4 ], [(t bpy)2 Rh(Cl)2 ][BAr′4 ], [(t bpy)2 Rh(Me)2 ][BAr′4 ], [(t bpy)2 Rh(Me)( I)][BAr′4 ], and [(t bpy)2 Rh(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. [ABSTRACT FROM AUTHOR]- Published
- 2013
- Full Text
- View/download PDF