Catalytic hydrogenolysis of an aryl-aryl carbon-carbon bond with a rhodium complex
- Univ. of Rochester, NY (United States)
Recent publications have brought renewed interest to the quest for homogeneous catalytic activation of carbon-carbon bonds. However, except for a few reports of biphenylene cleavage, the mechanism and scope of aryl-aryl C-C bond activation remains relatively uninvestigated. In the hope of overcoming the obstacle of weak M-C bonds, we used a rhodium system that should provide a thermodynamically favored C-C cleaved complex by making strong metal-aryl bonds. Reaction of (C[sub 5]Me[sub 5])Rh(PMe[sub 3])(Ph)(H) (1) with 1.5 equiv of biphenylene in cyclohexane-d[sub 12] at 65[degree]C resulted in the quantitative formation of (CC[sub 5]Me[sub 5])Rh(PMe[sub 3]) (biphenylenyl(H)) (2), along with a small amount of a red complex. The cleavage of the well-hidden carbon-carbon bond of biphenylene described relies both on a strained four-membered ring and on the formation of a stable pentametallacycle. The results show that C-H activation and [eta][sup 2] coordination are probably involved in the process leading to C-C bond cleavage, and valuable information can be obtained from studies of this system. 21 refs., 1 fig.
- DOE Contract Number:
- FG02-86ER13569
- OSTI ID:
- 7267441
- Journal Information:
- Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 116:8; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400201* -- Chemical & Physicochemical Properties
ALKANES
AROMATICS
CATALYSIS
CHEMICAL BONDS
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
CYCLOALKANES
CYCLOHEXANE
DIFFRACTION
HYDROCARBONS
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RESONANCE
RHODIUM COMPLEXES
SCATTERING
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION