The reaction barrier of oxidative addition reactions is well-known to depend on the bite angle, that is, the ligand-metal-ligand angle in the catalytic complex. Using relativistic density functional theory and the chemically intuitive Activation Strain model, we explain how the bite angle in dicoordinated d10 transition metal complexes can be adjusted with the electronic and steric properties of the metal center and ligands, without using chelating ligands of varying chain length. To this end, we present a detailed bonding mechanism in d10 ML2 complexes in terms of molecular orbital theory, for different combinations of metal center and ligands. We show that, and explain why, some dicoordinated d10 ML2complexes adopt bent geometries.Secondly, we briefly discuss the effect of tuning the bite angle of the catalytic complex on the energy profile of the oxidative addition of methane to a variety of catalytic complexes.

Bite angles in catalytic bond activation: Steric and electronic tuning

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.