Quantum mechanical study of the alkoxide-independent pathway of reductive elimination of C-O from palladium ( p-cyanophenyl) neopentoxide complex.

In this study the alkoxide-independent pathway of reductive elimination of C-O from palladium ( p-cyanophenyl) neopentoxide complex in THF at 47 °C was investigated theoretically by use of density functional theory and the solvent polarized continuum model. On the basis of experimental results a two-pathway mechanism had been proposed: a concerted process (path a) and a two-step process (path b) initiated by inner-sphere attack of the alkoxide ligand on the ipso-carbon atom of the palladium-bound aryl group (step 1) then Pd-C heterolysis to form p-neopentoxybenzonitrile (step 2). The activation energies of the two pathways were calculated by use of the quantum mechanical approach and compared with each other and with experimental results. [ABSTRACT FROM AUTHOR]