Transition metal activation and functionalization of carbon-hydrogen bonds

Technical Report · Sat Jun 01 00:00:00 EDT 1991

OSTI ID:5679034

Jones, W D

This project is directed towards 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 towards the conversion of hydrocarbons into functionalized products of potential use to the chemical industry. In the past two years, advances have been made in both understanding the interactions of hydrocarbons with metals and in the functionalization of hydrocarbons. Major advances 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 isonitrile pyrazolylborates for alkane and arene C-H bond activation. A new, labile, carbodiimide precursor has been developed for these studies. (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 facilely than thermal reductive elimination of H{sub 2}. (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. Thiophene, however, undergoes C-S bond oxidative addition, and the mechanism of activation has been shown to proceed through sulfur coordination prior to C-S insertion. 43 refs., 9 figs., 4 tabs.

• Research Organization: Rochester Univ., NY (USA)
• Sponsoring Organization: USDOE; USDOE, Washington, DC (USA)
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 5679034
• Report Number(s): DOE/ER/13569-6; ON: DE91014261
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
AROMATICS
CHEMICAL ACTIVATION
HETEROCYCLIC COMPOUNDS
ACTIVATION ENERGY
CHEMICAL REACTION YIELD
ISONITRILES
NMR SPECTRA
ORGANOMETALLIC COMPOUNDS
PHOTOLYSIS
RHODIUM COMPLEXES
STRUCTURAL CHEMICAL ANALYSIS
X-RAY DIFFRACTION
CARBONIC ACID DERIVATIVES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DECOMPOSITION
DIFFRACTION
ENERGY
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
SCATTERING
SPECTRA
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties
400500 - Photochemistry