Transition metal activation and functionalization of C-H bonds. Progress report, June 1, 1983-May 31, 1984
The initial year of this project has been directed at better understanding the mechanism of activation of carbon-hydrogen bonds by transition metal complexes. Our studies have focused upon derivatives of the a rhodium complex, and have provided a great deal of information about the mechanism and thermodynamics of C-H bond activation. Our approach has been to synthesize both aryl and alkyl derivatives of the type (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(R)H. Surprisingly, the aryl derivatives are stable up to +60/sup 0/C whereas the alkyl derivatives undergo elimination of alkane at -20/sup 0/C. Our studies indicate that the aryl complexes are in fact in equilibrium with an eta/sup 2/-arene derivative, affording them with an overall greater stability than the alkyl complexes. Kinetic and thermodynamic experiments indicate that the rhodium-phenyl bond is approx. 13 Kcal/mole stronger than the rhodium-methyl bond. It is shown that, unlike alkanes, arenes coordinate prior to activation. 1 figure.
- Research Organization:
- Rochester Univ., NY (USA). Dept. of Chemistry
- DOE Contract Number:
- AC02-83ER13095
- OSTI ID:
- 5319237
- Report Number(s):
- DOE/ER/13095-1; ON: DE84006343
- Country of Publication:
- United States
- Language:
- English
Similar Records
Transition metal activation and functionalization of C-H bonds. Progress report, June 1, 1984-May 31, 1985
Mechanism and thermodynamics of alkane and arene carbon-hydrogen bond activation in (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(R)H
Related Subjects
400201* -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACTIVATION ENERGY
ALKANES
AROMATICS
CHEMICAL BONDS
COMPLEXES
ENERGY
HYDROCARBONS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHYSICAL PROPERTIES
RESEARCH PROGRAMS
RHODIUM COMPLEXES
STABILITY
SYNTHESIS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES