Transition metal activation and functionalization of carbon-hydrogen bonds: Progress report, December 1, 1988--November 30, 1989

Technical Report · Thu Jun 01 04:00:00 EDT 1989

DOI:https://doi.org/10.2172/6255980· OSTI ID:6255980

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. Our goals during the grant period 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. These studies will also contribute toward the formulation of a unified theory of C-H bond activation that applies to other transition metal complexes. The specific complexes involved in these studies 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/. In the third year of this project, significant advances have been made in the observation of /eta//sup 2/-arene complexes of ((C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)). The complex (C/sub 5/Me/sub 5/)Rh(PMe/sub 3/)(/eta//sup 2/-phenanthrene) has been structurally characterized. Several other /eta//sup 2/-complexes have also been prepared. 17 refs., 4 tabs.

• Research Organization: Rochester Univ., NY (USA). Dept. of Chemistry
• DOE Contract Number: FG02-86ER13569
• OSTI ID: 6255980
• Report Number(s): DOE/ER/13569-3; ON: DE89012949
• Country of Publication: United States
• Language: English

Related Subjects

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