Abstract
The reaction mechanisms of the oxidation of 1,2-diphenylhydrazine by iodine have been examined using semiempirical and density functional theory methods, the oxidation proceeded via two independent pathways that can be separately monitored. One pathway involved the chain multistep mechanism. The other pathway occurred via a one-step mechanism in which a “cyclic” activated complex was formed which on disproportionation gave the products. The one-step “cyclic” activated complex mechanism proceeds more rapidly than the chain multistep mechanism. The results were explained by analyses based on computational energetics of the optimised reactants, intermediates, transition states, and products of the reaction of iodine with 1,2-diphenylhydrazine.
Highlights
1,2-Diphenylhydrazine is used as an antisludging additive to motor oil, a desuckering agent for tobacco plants, a reductant in the reclamation of rubber, a component of experimental organometallic polymers, an ingredient in photochromic resin compositions, and a component in polymerization reactions [1, 2]
In theoretical studies using ab initio or density functional theory (DFT) methods, adequate choices of a theoretical method and a basis set are very important in obtaining reliable results
In the present paper we report the results of a computational studies on the mechanism of the oxidation of 1,2diphenylhydrazine, a derivative of hydrazine by iodine, which is important per se and helps to shed light on the general mechanisms of oxidation of the –NH–NH, by iodine
Summary
1,2-Diphenylhydrazine is used as an antisludging additive to motor oil, a desuckering agent for tobacco plants, a reductant in the reclamation of rubber, a component of experimental organometallic polymers, an ingredient in photochromic resin compositions, and a component in polymerization reactions [1, 2]. Semiempirical models AM1, PM3, and MNDO are often used in computational chemistry because they allow study of systems that are out of reach of the more accurate methods These models are used for systems that contain elements beyond 4th row of the periodic table [30,31,32,33,34,35]. Heavy elements like iodine have a large number of core electrons which are in general less important for the chemical reactivity and bonding modes It needs a large number of basis sets or functions to describe the corresponding orbitals. Compounds containing iodine atom play very interesting and important roles in many chemical reactions, especially in the life sciences Despite the challenges, this makes the study of Iodine quite interesting
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