Phosphorylinitrile oxides. 7. Quantum chemical study of the dimerization of nitrile oxides

Autor:	V. A. Pavlov, B. I. Gorin, A. I. Kurdyukov
Rok vydání:	1994
Předmět:	Quantum chemical chemistry.chemical_compound Nitrile Acetonitrile oxide Chemistry Organic Chemistry Potential energy surface Oxide MNDO Molecule Singlet state Photochemistry
Zdroj:	Chemistry of Heterocyclic Compounds. 30:1101-1105
ISSN:	1573-8353 0009-3122
DOI:	10.1007/bf01171174
Popis:	A semiempirical MNDO calculation was carried out for the singlet potential energy surface for the dimerization of acetonitrile oxide leading to dimethylfuroxane. The dimerization of nitrile oxides proceeds by a two-step mechanism. The rate-limiting step is formation of a dinitrosoethylene intermediate. A semiempirical AMI calculation was carried out to study the effect of phosphoryl substituents on formation of the transition state of the rate-limiting step in the dimerization of dimethoxyphosphorylnitrile oxide. Independently of the initial orientation of the two phosphorylnitrile oxide molecules, a gauche-oriented dimerica species is formed in the first step in the dimerization. There is hardly any specific effect ofthe phosphoryl substituents in the first step of phosphorylnitrile oxide dimerization.
Databáze:	OpenAIRE
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