title: Nitrosobenzene dimerizations as a model system for studying solid-state reaction mechanisms.
abstract: Thermal dimerization of nitroso compounds in the solid state was investigated by using para-substituted nitrosobenzenes as model compounds. A mechanism that includes the interplay of topochemical reaction trajectories and phase transfer was proposed on the basis of FT-IR spectroscopic kinetics, time-resolved powder diffraction, and low-temperature X-ray structure determination. From shapes of the kinetic curves analyzed on the basis of the Avrami model, it was found that phase transfer could be triggered by a dimerization reaction of para-substituted nitrosobenzene to azodioxide, which, in turn, can be caused by different packing factors such as disorder in the starting nitroso monomer crystals. Since the represented model can be extended to a broad series of compounds, we propose it as a general method for investigations of solid-state reaction mechanisms.
authors.affiliation: Department of Chemistry, Faculty of Science, University of Zagreb, Strossmayerov trg 14, 10000 Zagreb, Croatia. vancik@rudjer.irb.hr
authors.forename: Hrvoj
authors.initials: H
authors.lastname: Vancik
authors.forename: Vesna
authors.initials: V
authors.lastname: Simunic-Meznaric
authors.forename: Ernest
authors.initials: E
authors.lastname: Mestrovic
authors.forename: Ivan
authors.initials: I
authors.lastname: Halasz