We investigated the effect of variation of the metal center for the oxidative addition of methane to a large number of transition metal catalysts with the general formula MLn. For the metal center M we employed nickel, palladium and platinum from group 10, as well as their iso-electronic metal centers from group 9 and 11, namely Co�, Rh�, Ir� and Cu+, Ag+ and Au+. We investigated the reactivity of bare metal centers, and mono- and bisligated catalysts, employing NH3, PH3 or CO as ligands. Using density functional theory and the Activation Strain Model, we obtained a rather complete insight into the effect of metal variation on oxidative addition reactions. Our analyses show that variation of the metal center has a profound influence on the barriers, comparable to ligand effects. Understanding these effects and their interplay is valuable for designing catalysts, custom-tailored to the desired selectivity and efficiency.

Effect of metal variation on oxidative addition: Perspectives from the activation strain model

245th National Meeting (2013)

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