Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds

We report here unambiguous experimental validation of this hypothesis: Detailed kinetic measurements demonstrate that stretching phosphotriesters accelerates dissociation of the unloaded phosphorus-oxygen bond orthogonal to the pulling axis, whereas stretching organosiloxanes inhibits dissociation of the aligned loaded silicon-oxygen bonds. Qualitatively, the outcome is determined by phosphoester elongation and siloxane contraction along the pulling axis in the respective rate-determining transition states. Quantitatively, the results agree with a simple mechanochemical kinetics model.

Source: ScienceNOW - July 20, 2017 Category: Science Authors: Akbulatov, S., Tian, Y., Huang, Z., Kucharski, T. J., Yang, Q.-Z., Boulatov, R. Tags: Chemistry reports Source Type: news