Data from: Allosteric control of olefin isomerization kinetics via remote metal binding and its mechano-chemical analysis

Allosteric control of reaction thermodynamics is well understood, but the mechanisms by which changes in local geometries of receptor sites lower activation reaction barriers in electronically uncoupled, remote reaction moieties remain relatively unexplored. Here we report a molecular scaffold in which the rate of thermal E-to-Z isomerization of an alkene increases by a factor of as much as 10^4 in response to fast binding of a metal ion to a remote receptor site. A mechanochemi-cal model of the olefin coupled to a compressive harmonic spring reproduces the observed accel-eration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally generalization of mechanochemical kinetics to compressive loads and demonstrates that the formalism of force-coupled reactivity offers a productive framework for the quantitative analysis of the molecular basis of allosteric control of reaction kinetics. Important differences in the effects of compressive vs. tensile force on the kinetic stabilities of molecules are discussed. The characterization and kinetic data generated in this study are deposited herein.

别构调控（allosteric control）反应热力学的机制已得到充分阐明，但受体位点局部几何变化如何降低电子解耦的远端反应基团的反应活化能垒，这一机制仍相对未被深入探索。在此，我们报道一种分子骨架（molecular scaffold）：当金属离子快速结合至远端受体位点时，烯烃的热致E→Z异构化速率最高可提升10⁴倍。将烯烃与压缩性简谐弹簧耦合的机械化学（mechanochemical）模型可定量复现所观测到的加速效应，将本次研究的异构化反应纳入为数不多的被证实对外界压缩力敏感的反应范畴。本研究验证了机械化学动力学可推广至压缩载荷的实验结论，并证明力耦合反应性的形式体系为定量分析别构调控反应动力学的分子基础提供了极具价值的研究框架。本文还讨论了压缩力与拉伸力对分子动力学稳定性影响的显著差异。本研究生成的表征数据与动力学结果已随本文一并存档。