Selective C-H and C-C Bond Activation: Electronic Regimes as a Tool for Designing d10 MLn Catalysts

We wish to understand how a transition-metal catalyst can be rationally designed so as to selectively activate one particular bond in a substrate, herein, C-H and C-C bonds in ethane. To this end, we quantum chemically analyzed the activity and selectivity of a large series of model catalysts towards ethane and, for comparison, methane, by using the activation strain model and quantitative molecular orbital theory. The model catalysts comprise d(10) MLn complexes with coordination numbers n=0, 1, and 2; metal centers M=Co-, Rh-, Ir-, Ni, Pd, Pt, Cu+, Ag+, and Au+; and ligands L=NH3, PH3, and CO. Our analyses reveal that rather subtle electronic differences between bonds can be exploited to induce a lower barrier for activating one or the other, depending, among other factors, on the catalyst's electronic regime (i.e., s-regime versus d-regime catalysts). Interestingly, the concepts and design principles emerging from this work can also be applied to the more challenging problem of differentiating between activation of the C-H bonds in ethane versus those in methane.