CALCULATION OF LIGAND NMR CHEMICAL-SHIFTS IN TRANSITION-METAL COMPLEXES USING AB-INITIO EFFECTIVE-CORE POTENTIALS AND DENSITY-FUNCTIONAL THEORY

A combination of ab initio effective-core potentials and sum-over-stat es density functional perturbation theory has been used to calculate C -13 NMR chemical shifts in a series of transition-metal organometallic complexes, up to and including sixth-period species. Thus, for the fi rst time both electron correlation and scalar relativistic effects hav e been included in chemical shift calculations. The good agreement wit h experiment indicates that this methodology is a powerful new tool to predict and rationalize ligand NMR chemical shifts in organometallic and inorganic transition-metal complexes. Sources of remaining discrep ancies to experiment are discussed.