Transition Metal Activation and Functionalization of C-H Bonds: Progress Report, December 1, 1987-November 30, 1988.

摘要

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. (ERA citation 13:047073)