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



Wang, Liqi, Yu, Yichen, Razgoniaev, Anton O, Johnson, Patricia N, Wang, Chenxu, Tian, Yancong ORCID: 0000-0001-9075-0363, Boulatov, Roman ORCID: 0000-0002-7601-4279, Craig, Stephen L and Widenhoefer, Ross A
(2020) Mechanochemical Regulation of Oxidative Addition to a Palladium(0) Bisphosphine Complex. Journal of the American Chemical Society.

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Abstract

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.

Item Type: Article
Depositing User: Symplectic Admin
Date Deposited: 28 Sep 2020 08:09
Last Modified: 04 Sep 2022 07:15
DOI: 10.1021/jacs.0c08506
URI: https://livrepository.liverpool.ac.uk/id/eprint/3102536