| Abstract |
Metal-eta(5)-cyclopentadienyl (M-Cp) and metal-eta(5)-pyrrolyl (M-pyr) bond dissociation enthalpies in group 4 complexes were determined from DFT/B3LYP calculations with a VTZP basis set. Thermochemical cycles involving calculated enthalpies of ligand exchange reactions and experimental values of ligand electron affinities and M-Cl bond dissociation enthalpies were applied to [M(eta(5)-X)Cl-3] piano stool complexes (M = Ti, Zr, Hf, X = pyr, Cp), allowing a comparative study of those metal-ligand bond strengths. The results indicate that both ligands establish weaker bonds with Ti than with the heavier elements, Zr and HE Very similar bond dissociation enthalpies were obtained for pyrrolyl and cyclopentadienyl (within 1 kcal mol(-1)), suggesting that the well known difference in reactivity between those families of complexes should derive from kinetic rather than thermodynamic causes. (c) 2005 Elsevier B.V. All rights reserved. |
