Computational study of methane activation by mercury(II) complexes

✍ Scribed by Cundari, Thomas R.; Yoshikawa, Akihiko

• Publisher: John Wiley and Sons
• Year: 1998
• Tongue: English
• Weight: 337 KB
• Volume: 19
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(199806)19:8<902::aid-jcc9>3.0.co;2-t

✦ Synopsis

A computational investigation of methane activation by Hg II Ž . 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 Hg II complexes cover a wide range of values for different ligands. This diversity suggests that the kinetics and thermodynamics of methane Ž . activation by Hg II and related medium-valent complexes can be tailored through rational modification of the ligand environment. Calculated activation Ž . 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.