Matrix isolation FTIR spectroscopical study of ethene secondary ozonide

Abstract

Abstract:A new method is used for the separation of ethene secondary ozonide (SOZ) from the other products of ethene ozonization reaction. The reaction was performed in the neat films of the reactants at 77 K. Ethene SOZ was separated from other products of the reaction by vacuum distillation at 190-210 K and analyzed by means of the matrix isolation IR absorption spectroscopy. Spectroscopic data from photolysis of the matrix isolated ozonide was used as an argument for assignment of the infrared spectral bands either to ethene SOZ or to other products of the reaction. The spectra of ethene SOZ isolated in the Ar matrix were analyzed by combining experimental results with the theoretical calculations performed at the MP2 6-311+G (3df, 3pd) level. A new assignment of some experimental fundamental bands is proposed taking in to account the Fermi resonance between CH stretch and the five membered ring vibrations. For the first time more than 30 weak infrared absorption bands were observed and assigned to various combination vibrations and overtones. By using new spectral information concerning the overtones and the combination bands it is concluded that the dissociation of unstable ethene SOZ involving breaking of any of the four CO bonds of the five membered ring of ethene SOZ has low probability. Dissociation of the ring starts from breaking of the OO bond.

Chrysalis-Like Graphene Oxide Decorated Vanadium-Based Nanoparticles: An Extremely High-Power Cathode for Magnesium Secondary Batteries

“…[38][39][40][41][42] Finally, several other peaks which are attributed to the GO matrix are present in the vibrational spectra. 32,33,35,36,[43][44][45][46] In the last region (III), below 1050 cm −1 , the peaks are assigned to the vibrational modes of different V-X (X = −O − NH 4 + , SO 4 2− , Cl − ) functional groups 31,37,[47][48][49][50] and of a rotational lattice mode of the ammonium ions [38][39][40][41][42] (see Table I).…”

Computational Study of the Dissociation Reactions of Secondary Ozonide

“…SOZ is formed when a stabilized Criegee intermediate undergoes a 1,3-dipolar cycloaddition to the carbonyl compound, as shown in Figure 1. SOZ is more stable than primary ozonide and exhibits a sufficiently long lifetime [5][6][7]. The formation of SOZ from alkenes has been reported in numerous studies [8,9] with a prime focus on the formation and relative stability of SOZs resulting from the ozonolysis of selected cyclic monoterpenes (C 10 H 16 ) [10] taking place in both a gas and a liquid phase.…”

“…A schematic of the initial reaction pathways for the ozonolysis of ethene is depicted in Figure 1. Herein, primary ozonide (POZ), carbonyl oxide, and secondary ozonide (1,2,4-trioxolane, SOZ) are formed as transitory products of the reaction [5]. Carbonyl oxide and formaldehyde react to produce the ethene secondary ozonide that involves the formation of a van der Waals complex on the reaction coordinate before reaching the transition state.…”

The Kinetics of Tetramethylethene Ozonolysis: Decomposition of the Primary Ozonide and Subsequent Product Formation in the Condensed Phase

“…To study the POZ and its decomposition kinetics and products, one can observe the ozonolysis of condensed alkenes on a cryogenic surface. The POZ has been observed on a cold surface using various methods, including microwave spectroscopy, , nuclear magnetic resonance, ,,, and infrared spectroscopy. ,,− We have designed an apparatus to perform kinetic studies of primary ozonide decomposition with real-time Fourier transform infrared spectroscopy (FTIR).…”

“…The POZ has been observed on a cold surface using various methods, including microwave spectroscopy, 38,39 nuclear magnetic resonance, 13,38,40,41 and infrared spectroscopy. 17,38,[42][43][44][45] We have designed an apparatus to perform kinetic studies of primary ozonide decomposition with real-time Fourier transform infrared spectroscopy (FTIR).…”