S. A. Grabovskii, I. S. Odin, A. A. Golovanov, A. V. Antipin, R. L. Safiullin
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引用次数: 0
Abstract
The bond dissociation enthalpy of the N–H bond was calculated for the following compounds: 1-((E)-1,5-diphenylpent-1-en-4-yn-3-ylidene)-2-(o-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine, 1-((E)-1-phenylpent-1-en-4-yn-3-ylidene)-2-(p-tolyl)hydrazine, 1-((E)-1-(4-methoxyphenyl)-5-trimethylsilyl-1-en-4-yn-3-ylidene)-2-phenylhydrazine, and 1-((E)-1-(toiphenyl-2)-5-phenylpent-1-en-4-yn-3-ylidene)-2-phenylhydrazine. The calculations were performed by the M06-2X/6-311+G(2df,2pd)//B3LYP/6-31G(d) method using the homodesmotic approach. The bond dissociation enthalpy is lower than 77 kcal/mol for all the cross-conjugated hydrazone derivatives under study. The experimental rate constants for the reactions of the derivatives with peroxyl radicals in chlorobenzene during the initiated styrene oxidation are comparable to those of aromatic amines and are in the range (1.1–2.5) × 105 M−1 s−1. The stoichiometric inhibition coefficient depends on the structure of the derivatives and varies from 0.7 to 1.9. The inhibition is discussed within the framework of the radical mechanism.
期刊介绍:
Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.