Transition metal activation and functionalization of C-H bonds. Progress report, June 1, 1984-May 31, 1985

Technical Report · Thu Jan 31 23:00:00 EST 1985

OSTI ID:6064658

Jones, W D

The second year of this project has been directed towards the continued investigation of the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers. The major accomplishment of this past year has been to elucidate the intramolecular activation reaction that was considered to be a major competing side reaction in the systems proposed for C-H bond activation. The mechanism and thermodynamics of alkane and arene C-H bond activation has been investigated by the reactive intermediate ((C/sub 5/Me/sub 5/)Rh(PMe/sub 2/R)), where R = benzyl or propyl. Earlier studies showed that arene activation occurs by way of initial coordination in a dihapto fashion. Kinetically, intermolecular alkane activation competes with arene activation, whereas arene activation is favored thermodynamically by 7 kcal/mole. In the most recent studies, the intramolecular activation of C-H bonds of alkyl and aryl groups is found to compete kinetically with intermolecular activation of neat solvent. The difference between the intra and intermolecular entropies of activation is not found to be a significant factor in determining intra vs intermolecular reaction. Thermodynamically, intramolecular activation is found to be favored.

• Research Organization: Rochester Univ., NY (USA)
• DOE Contract Number: AC02-83ER13095
• OSTI ID: 6064658
• Report Number(s): DOE/ER/13095-T1; ON: DE85006816
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALKANES
AROMATICS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL BONDS
CHEMICAL REACTIONS
COMPLEXES
HYDROCARBONS
ORGANIC COMPOUNDS
RESEARCH PROGRAMS
RHODIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES