Transition metal activation and functionalization of carbon-hydrogen bonds

Technical Report · Sun Jul 01 00:00:00 EDT 1990

OSTI ID:6712674

Jones, W D

This project is directed toward the continued investigation of the fundamental thermodynamic and kinetic factors that influence carbon-hydrogen bond activation at homogeneous transition metal centers. The project is also directed toward the conversion of hydrocarbons into functionalized products of potential use to chemical industry. In the past year, advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalized of hydrocarbons. Major advanced that have been made include: (1) We have found that RhCl(PR{sub 3}){sub 2}(CNR) complexes can catalyze the insertion of isonitriles into the C-H bonds of arenes upon photolysis. (2) We have also examined reactions of a series of arenes with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and begun to map out the kinetic and thermodynamic preferences for arene coordination. (3) We have begun to examine the reactions of rhodium pyrazolylborates for isonitrile functionalization of C-H bonds. (4) We have completed studies of the reactions of (C{sub 5}Me{sub 5})Rh(PMe{sub 3})H{sub 2} with D{sub 2} and PMe{sub 3} that indicate that both {eta}{sup 5} {yields} {eta}{sup 3} ring slippage and metal to ring hydride migration occur more faciley than reductive elimination of H{sub 12}. (5) We have examined the reactions of heterocycles with (C{sub 5}Me{sub 5})Rh(PMe{sub 3})PhH and found that pyrrole and furan undergo C-H or N-H activation.

• Research Organization: Rochester Univ., NY (USA)
• Sponsoring Organization: DOE/ER
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 6712674
• Report Number(s): DOE/ER/13569-5; ON: DE90015826
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHODIUM COMPLEXES
CATALYTIC EFFECTS
ALKANES
AROMATICS
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
FREE ENERGY
HYDROCARBONS
MOLECULAR STRUCTURE
PROGRESS REPORT
THERMODYNAMICS
COMPLEXES
DOCUMENT TYPES
ENERGY
KINETICS
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties