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Pt II and Rh III Hydrocarbyl Complexes Bearing Coordinated Oxygen Atom Delivery Reagents
Author(s) -
Webb Joanna R.,
Figg Travis M.,
Otten Brooke M.,
Cundari Thomas R.,
Gunnoe T. Brent,
Sabat Michal
Publication year - 2013
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201300434
Subject(s) - chemistry , rhodium , trifluoromethanesulfonate , pyridine , bipyridine , organometallic chemistry , crystallography , reactivity (psychology) , reagent , oxygen atom , medicinal chemistry , bar (unit) , crystal structure , platinum , catalysis , stereochemistry , molecule , organic chemistry , medicine , physics , alternative medicine , pathology , meteorology
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 Pt II and Rh III complexes [( t bpy)Pt(Ph)(ONMe 3 )][BAr′ 4 ], [( t bpy)Pt(Ph)(OPy)][BAr′ 4 ], [( t bpy) 2 Rh(Me)(ONMe 3 )][BAr′ 4 ][OTf], and [( t bpy) 2 Rh(Me)(OPy)][BAr′ 4 ][OTF] (Ar′ = 3,5‐(CF 3 ) 2 C 6 H 3 , OPy = pyridine N ‐oxide) have been isolated and characterized by 1 H, 13 C, and 19 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 Pt II –R and Rh III –R bonds.