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Mechanochemically induced cross‐dimerizations of nitrosobenzenes. Kinetics and solid‐state isotope effects
Author(s) -
Maganjić Ana,
Šolić Ivan,
Milovac Srđan,
Halasz Ivan,
Biljan Ivana,
Vančik Hrvoj
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3256
Subject(s) - chemistry , kinetic isotope effect , kinetics , dissociation (chemistry) , solid state , solid surface , kinetic energy , reaction mechanism , photochemistry , organic chemistry , catalysis , chemical physics , deuterium , physics , quantum mechanics
Mechanical treatment (milling) of crystals of aromatic nitroso dimers (azodioxides) induces their dissociation and cross‐dimerizations. The mechanisms of these processes are discussed on the basis of kinetic studies and the solid‐state 15 N kinetic isotope effect, which is measured for the first time. By comparison with analogous processes in cocrystals and in melts, it appears that the reactions follow similar mechanism in which the surface deformations play the crucial role. The system can also be used as a model for a more general conceptual study of solid‐state reaction mechanisms. Copyright © 2013 John Wiley & Sons, Ltd.