In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2013, No. 25 ( 2013-09-02), p. 4515-4525
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 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.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2013.25
DOI:
10.1002/ejic.201300434
Language:
English
Publisher:
Wiley
Publication Date:
2013
detail.hit.zdb_id:
1475009-0
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