REGIOSELECTIVITY OF NUCLEOPHILIC-ATTACK ON [PD(ALLYL)(PHOSPHINE)(IMINE)]COMPLEXES - A THEORETICAL-STUDY

Extended Huckel calculations help rationalize the observed regioselect ivity of allylic alkylations catalyzed by Pd complexes containing eith er C-2-symmetric or electronically asymmetric bidentate chiral ligands . Mixing of the empty high-lying pi into the LUMO, made up most Ey of the antibonding combination between the d(x2-y2) and the allyl nonbon ding fragment orbitals, increases the electrophilicity of the carbon w ith the longest Pd-C bond as its weight in the LUMO increases.