Kinetic and thermodynamic selectively of alkane and arene C-H bonds by [(trispyrazolylborate)Rh(CNR)]
Conference
·
OSTI ID:141042
- Univ. of Rochester, NY (United States)
The rhodium trispyrozolylborate complex [tris(3,5-dimethylpyrazolyl)borate]Rh(CNneopentyl)({eta}{sup 2}-PhN=C=Nneopentyl) has been found to photochemically lose the carbodimide ligand with a quantum efficiency of near unity. The 16-electron fragment produced in this fashion adds to a variety of alkanes and arenes (pentane, cyclopentane, cyclohexane, benzene, and toluene) at room temperature. Methane can be activated thermally by exchange with the cyclohexane complex. Both benzylic and aromatic activation of toluene are seen. Competitive kinetic selectives for activation of the different C-H bonds and measurements of the rates of hydrocarbon reductive elimination have been used to establish the relative thermodynamic stabilities of the C-H activated complexes. A comparison of the relative of C-H and Rh-C bond strengths and the correlation between these values is made. The mechanism of the benzene oxidative addition will also be discussed.
- OSTI ID:
- 141042
- Report Number(s):
- CONF-930304--
- Country of Publication:
- United States
- Language:
- English
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