Computational study of methane activation by mercury(II) complexes

Abstract

A computational investigation of methane activation by HgII complexes is reported. Calculated geometries and energetics of Hg(II)-containing reactants and products are consistent with available experimental data for a wide range of diverse ligand types. Calculated reaction enthalpies and activation barriers for HgII complexes cover a wide range of values for different ligands. This diversity suggests that the kinetics and thermodynamics of methane activation by Hg(II) and related medium-valent complexes can be tailored through rational modification of the ligand environment. Calculated activation barriers and reaction enthalpies for methane activation by Hg(II) complexes indicates that harder, more electronegative, ligands are kinetically and thermodynamically preferred. Potential donor groups on the activating ligand can stabilize the transition state versus the ground state reactants and hence result in substantially lower methane activation barriers. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 902–911, 1998