Allosteric control of olefin isomerization kinetics via remote metal binding and its mechanochemical analysis.

ABSTRACT: 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 10⁴ in response to fast binding of a metal ion to a remote receptor site. A mechanochemical model of the olefin coupled to a compressive harmonic spring reproduces the observed acceleration quantitatively, adding the studied isomerization to the very few reactions demonstrated to be sensitive to extrinsic compressive force. The work validates experimentally the generalization of mechanochemic

SUBMITTER: Yu Y 

PROVIDER: S-EPMC10442431 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature