Yu, Yichen, Wang, Chenxu, Wang, Liqi, Sun, Cai-Li, Boulatov, Roman 
ORCID: 0000-0002-7601-4279, Widenhoefer, Ross A and Craig, Stephen L
(2021)
Force-modulated reductive elimination from platinum(ii) diaryl complexes.
CHEMICAL SCIENCE, 12 (33).
pp. 11130-11137.
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Abstract
Coupled mechanical forces are known to drive a range of covalent chemical reactions, but the effect of mechanical force applied to a spectator ligand on transition metal reactivity is relatively unexplored. Here we quantify the rate of C(sp<sup>2</sup>)-C(sp<sup>2</sup>) reductive elimination from platinum(ii) diaryl complexes containing macrocyclic bis(phosphine) ligands as a function of mechanical force applied to these ligands. DFT computations reveal complex dependence of mechanochemical kinetics on the structure of the force-transducing ligand. We validated experimentally the computational finding for the most sensitive of the ligand designs, based on MeOBiphep, by coupling it to a macrocyclic force probe ligand. Consistent with the computations, compressive forces decreased the rate of reductive elimination whereas extension forces increased the rate relative to the strain-free MeOBiphep complex with a 3.4-fold change in rate over a ∼290 pN range of restoring forces. The calculated natural bite angle of the free macrocyclic ligand changes with force, but <sup>31</sup>P NMR analysis and calculations strongly suggest no significant force-induced perturbation of ground state geometry within the first coordination sphere of the (P-P)PtAr<sub>2</sub> complexes. Rather, the force/rate behavior observed across this range of forces is attributed to the coupling of force to the elongation of the O⋯O distance in the transition state for reductive elimination. The results suggest opportunities to experimentally map geometry changes associated with reactions in transition metal complexes and potential strategies for force-modulated catalysis.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | Bioengineering |
| Divisions: | Faculty of Science and Engineering > School of Physical Sciences |
| Depositing User: | Symplectic Admin |
| Date Deposited: | 08 Dec 2021 14:58 |
| Last Modified: | 14 Mar 2024 20:03 |
| DOI: | 10.1039/d1sc03182a |
| Open Access URL: | https://pubs.rsc.org/en/content/articlelanding/202... |
| Related URLs: | |
| URI: | https://livrepository.liverpool.ac.uk/id/eprint/3144966 |
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