FIRST-PRINCIPLES INTERPRETATION OF LIGAND ELECTROCHEMICAL (E(L)(L)) PARAMETERS - FACTORIZATION OF THE SIGMA-DONOR AND PI-DONOR AND PI-ACCEPTOR CAPABILITIES OF LIGANDS

The ligand electrochemical series, E(L)(L), has been developed for man y hundreds of ligands, and provides an accurate prediction of metal-ce ntered redox potentials for coordination complexes. Semiempirical meth ods are used in conjunction with second-order perturbation theory to p rovide a new method to factorize the E(L)(L) parameter and extract a n ew and general measure of the sigma- and pi-donating and pi-accepting properties of a ligand.