NDLI: Kinetics and mechanism of the highly efficient generation of singlet oxygen in dimethyldioxirane decomposition induced by the chloride ion

Content Provider	Springer Nature Link
Author	Ovchinnikov, M. Yu. Kazakov, D. V. Khursan, S. L.
Copyright Year	2012
Abstract	The decomposition of dimethyldioxirane induced by the chloride anion has been investigated by methods of infrared chemiluminescence and quantum chemistry. The reaction leads to efficient generation of singlet excited molecular oxygen $^{1}$O$_{2}$ (the excitation yield in acetone is 61%). A mechanism of peroxide decomposition is proposed in which the key reactions are the addition of the chloride ion to an oxygen atom of dioxirane, resulting in dioxirane ring opening and the formation of the 2-chlorooxy-2-hydroxy propane alcoholate (k $_{1}$), and the interaction of the latter with another dimethyldioxirane molecule. This interaction results either in the formation of an adduct, which further decomposes to evolve $^{1}$O$_{2}$, and catalyst regeneration (k $_{2}$) or in the formation of the 2-chloroxyisopropyl radical, which leads to the irreversible consumption of the chloride ion catalyst (k $_{3}$). The decay kinetics of the infrared chemiluminescence of $^{1}$O$_{2}$ has been studied in a wide range of reactant concentrations. The temperature dependence of the rate constant of the reaction of dimethyldioxirane with the chloride ion has been determined by a kinetic analysis of the mechanism proposed: log($^{2}$ k $_{1}$) = (11.1 ± 0.7) − (46 ± 4)/Θ, where Θ = 2.3RT kJ/mol. Estimation of the ratio of the rates of the reaction of the 2-chlorooxy-2-hydroxy propane alcoholate with dimethyldioxirane via two pathways (k $_{3}$/k $_{2}$) has demonstrated that the fraction of the process involving electron transfer does not exceed 1.5% under the experimental conditions examined. Nevertheless, the latter reaction, which withdraws the chloride ion from the catalytic cycle of dimethyldioxirane decomposition yielding singlet oxygen, has a marked effect on the overall kinetics of the process.
Starting Page	42
Ending Page	53
Page Count	12
File Format	PDF
ISSN	00231584
Journal	Kinetics and Catalysis
Volume Number	53
Issue Number	1
e-ISSN	16083210
Language	English
Publisher	SP MAIK Nauka/Interperiodica
Publisher Date	2012-02-14
Publisher Place	Dordrecht
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Catalysis Physical Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry Catalysis Modeling and Simulation Computer Science Applications

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