We wish to understand how a transition-metal catalyst can be rationally designed such as to selectively activate one particular bond in a substrate. To this end, we quantum chemically analyze the activity and selectivity of various model catalysts towards different types of substrates, using the activation strain model and quantitative molecular orbital theory. 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).
Understanding the Differences Between Iron and Palladium in Cross-Coupling Reactions
X. Sun, M. V. J. Rocha, T. A. Hamlin, J. Poater, F. M. Bickelhaupt
Role of Steric Attraction and Bite-Angle Flexibility in Metal-Mediated C–H Bond Activation
L. P. Wolters, R. Koekkoek, F. M. Bickelhaupt
New Concepts for Designing d10-M(L)n Catalysts: d Regime, s Regime and Intrinsic Bite-Angle Flexibility
L. P. Wolters, W. J. van Zeist, F. M. Bickelhaupt