Kinetics of dimerization of C- nitroso ccompounds in solid state

Varga, Katarina (2015) Kinetics of dimerization of C- nitroso ccompounds in solid state. Doctoral thesis, Faculty of Science > Department of Chemistry.

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Abstract

Dimerization of nitroso compounds has been used as a suitable model for kinetic studies of organic reactions in crystals. The influence of the surface defects caused by sublimation of molecules on the dimerization rates of 4-bromo (1) and 4-iodonitrosobenzene (4) has been investigated in various topochemical environments: from monomer molecules in the crystal lattice prepared by photolysis to the randomly oriented monomer molecules in a thin layer. The activation energy for the dimerization of 1 has been estimated from the temperature dependence of the reaction rate. Most of the literature on the isomerisation in the solid state is focused on the photochemical reactions and very little attention is paid to the thermally induced reactions. In this work we have been investigated the solid state thermal isomerization of the E-3-halogenonitrosobenzenes in their Z-dimeric analogues. It has been shown that azodioxide Z-E isomerization in the solid state could occur without the formation of the free nitroso molecules. Such „unimolecular” isomerization has not yet been observed. The reaction has been studied by measuring the reaction rate of dimerization in different topochemical conditions by exploring the isomerization of E-3-chloro (2) and E-3-bromonitrosobenzene (3) at different temperatures and also by analyzing activation parameters for the solid state dimerization and isomerization.

Item Type: Thesis (Doctoral thesis)
Keywords: dimerization, E-Z isomerization in the solid state, halogenonitrosobenzene, kinetics, solid state, sublimation, topochemistry
Supervisor: Vančik, Hrvoj
Date: 2015
Number of Pages: 139
Subjects: NATURAL SCIENCES > Chemistry > Organic Chemistry
Divisions: Faculty of Science > Department of Chemistry
Depositing User: Zdenka Kuri
Date Deposited: 12 Jun 2015 12:58
Last Modified: 12 Jun 2015 12:58
URI: http://digre.pmf.unizg.hr/id/eprint/4048

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