Mechanochemical Regulation of Oxidative Addition to a Palladium(0) Bisphosphine Complex.

Here, we report the effect of force applied to the biaryl backbone of a bisphosphine ligand on the rate of oxidative addition of bromobenzene to a ligand-coordinated palladium center. Local compressive and tensile forces on the or-der of 100 pN were generated using a stiff stilbene force probe. A compressive force increases the rate of oxidative addition, whereas a tensile force decreases the rate, relative to that of the parent complex of strain-free ligand. Rates vary by a factor of ~6 across ~340 pN of force applied to the complexes. The crystal structures and DFT calculations support that force-induced perturbation of the geometry of the reactant is negligible. The force-rate relationship ob-served is mainly attributed to the coupling of force to nuclear motion comprising the reaction coordinate. These observations inform the development of catalysts whose activity can be tuned by an external force that is adjusted within a catalytic cycle