Transition metal activation and functionalization of C-H bonds: Progress report, December 1, 1987-November 30, 1988

Technical Report · Mon Aug 01 00:00:00 EDT 1988

OSTI ID:7144016

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 chemical industry. Goals will be 1) to identify new transition metal complexes capable of activating arene and alkane C-H bonds, 2) to quantitatively evaluate the kinetic and thermodynamic stability of these complexes, and 3) to examine routes for functionalization of the activated hydrocarbons. Specific complexes involved are derivatives of the formulation (C/sub 5/Me/sub 5/)Rh(PR/sub 3/)(R)H, Fe(PMe/sub 3/)/sub 2/(CNR)/sub 3/, Ru(PR/sub 3/)/sub 4/(R)H, and Rh(CNR)/sub 3/H. Functionalization will focus upon isocyanide and acetylene insertion reactions. New compounds that activate hydrocarbon C-H bonds include HRe(PR/sub 3/)/sub 5/, HRe(PR/sub 3/)/sub 2/(CNR)/sub 3/, CpRe(PR/sub 3/)H/sub 4/, CpRe(PR/sub 3/)/sub 2/H/sub 2/, (/eta//sup 6/-C/sub 6/H/sub 6/)Re(PPh/sub 3/)/sub 2/H, and MnH/sub 3/(dmpe)/sub 2/. The latter complex is found to be an /eta//sup 2/-dihydrogen complex. The new complexes RhCl(P(i-Pr)/sub 3/)/sub 2/(CNCH/sub 2/CMe/sub 3/) and (trispyrazolylborate)Rh(CNR)/sub 2/ are shown to be active for the activation and functionalization of aromatic C-H bonds. 10 figs., 1 tab.

• Research Organization: Rochester Univ., NY (USA). Dept. of Chemistry
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 7144016
• Report Number(s): DOE/ER/13569-2; ON: DE88014626
• Resource Relation: Other Information: Portions of this document are illegible in microfiche products
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RHENIUM COMPLEXES
CATALYTIC EFFECTS
RHODIUM COMPLEXES
CHEMICAL ACTIVATION
RUTHENIUM COMPLEXES
ACETYLENE
AROMATICS
CARBON
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CYANIDES
FREE ENERGY
HYDROGEN
IRON COMPLEXES
MOLECULAR STRUCTURE
PROGRESS REPORT
RADIATION EFFECTS
SPECIFICITY
THERMODYNAMICS
TRANSITION ELEMENTS
ALKYNES
COMPLEXES
DOCUMENT TYPES
ELEMENTS
ENERGY
HYDROCARBONS
KINETICS
METALS
NONMETALS
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
REACTION KINETICS
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties