Evidence for methane {sigma}-complexes in reductive elimination reactions from Tp{prime}Rh(L)(CH{sub 3})H
Journal Article
·
· Journal of the American Chemical Society
- Univ. of Rochester, NY (United States). Dept. of Chemistry
Two sets of experiments are describes that provide indirect evidence for the involvement of alkane {sigma}-complexes in oxidative addition/reductive elimination reactions of Tp{prime}Rh(L)(R)H complexes (Tp{prime} = tris-3,5-dimethylpyrazolylborate, L = CNCH{sub 2}CMe{sub 3}). First, the methyl deuteride complex Tp{prime}Rh(L)(CH{sub 3})D is observed to rearrange to Tp{prime}Rh(L)(CH{sub 2}D)H prior to loss of CH{sub 3}D. Similarly, Tp{prime}Rh(L)(CD{sub 3})H rearranges to Tp{prime}Rh(L)(CD{sub 2}H)D prior to loss of CD{sub 3}H. Second, the rate of elimination of methane from Tp{prime}Rh(L)(CH{sub 3})H in benzene/perfluorobenzene solvent mixtures is found to be dependent upon the concentration of benzene, indicating an associative component to the reductive elimination of methane. Both of these processes, and their rates, are accommodated by the reversible formation of alkane {sigma}-complexes prior to dissociation of alkane.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-86ER13569
- OSTI ID:
- 684320
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 16 Vol. 121; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
Similar Records
Carbon-hydrogen and carbon-carbon bond activation of cyclopropane by a hydridotris(pyrazolyl)borate rhodium complex
Energetics of homogeneous intermolecular vinyl and allyl carbon-hydrogen bond activation by the 16-electron coordinatively unsaturated organometallic fragment [Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})]
Photolysis of Tp[prime]Rh(CN-neopentyl)([eta][sup 2]-PhN[double bond]C[double bond]N-neopentyl) in alkanes and arenes: Kinetic and thermodynamic selectivity of [Tp[prime]Rh(CN-neopentyl)] for various types of C-H bonds
Journal Article
·
Mon Sep 28 00:00:00 EDT 1998
· Organometallics
·
OSTI ID:315969
Energetics of homogeneous intermolecular vinyl and allyl carbon-hydrogen bond activation by the 16-electron coordinatively unsaturated organometallic fragment [Tp{prime}Rh(CNCH{sub 2}CMe{sub 3})]
Journal Article
·
Sun Feb 14 23:00:00 EST 1999
· Organometallics
·
OSTI ID:329263
Photolysis of Tp[prime]Rh(CN-neopentyl)([eta][sup 2]-PhN[double bond]C[double bond]N-neopentyl) in alkanes and arenes: Kinetic and thermodynamic selectivity of [Tp[prime]Rh(CN-neopentyl)] for various types of C-H bonds
Journal Article
·
Tue Jan 26 23:00:00 EST 1993
· Journal of the American Chemical Society; (United States)
·
OSTI ID:6539260