PtII and RhIII Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents

• Published in: European journal of inorganic chemistry 2013-09, Vol.2013 (25), p.4515-4525
• Main Authors: Webb, Joanna R., Figg, Travis M., Otten, Brooke M., Cundari, Thomas R., Gunnoe, T. Brent, Sabat, Michal
• Format: Article
• Language: English
• Subjects: Density functional calculations; Diffraction; Hydro­carbyl ligands; Insertion; Oxidants; Oxygen; Platinum; Rhodium; Spectrum analysis
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201300434

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. PtII and RhIII hydrocarbyl complexes with coordinated oxygen‐atom‐delivery reagents have been isolated. 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.