Theoretical study of acridane oxidation reactions / Grishina M. A.,Potemkin V. A.,Matern A. I. // JOURNAL OF STRUCTURAL CHEMISTRY. - 2008. - V. 49, l. 1. - P. 7-12.

ISSN/EISSN:

0022-4766 / нет данных

Type:

Article

Abstract:

The interactions of acridanes with oxidants were modeled using combined methods of quantum chemistry (DFT B3LYP/6-311G(d,p)), molecular mechanics, MERA model, and MOPS algorithm. The results of simulation are compared with XRD data, oxidation potentials of acridanes, and the reduction potentials of the products of the oxidation reaction. It is shown that elimination of the hydride anion by the reactions of acridanes with oxidants is a consequence of a two-step process; the first step is the transfer of electron density from the HOMO of acridane to the LUMO of the oxidant; the second step is hydrogen elimination from the acridane molecule due to hydrogen bonding with the oxygen atom of the oxidant. The details of the mechanism were established by modeling the acridane-oxidant complexes using the MOPS algorithm including the continuum model of the solvent. The logarithms of the rate constants of the processes depend on the structure parameters of the model complexes with correlation coefficients of at least 0.93.

Author keywords:

simulation; complexes; topological analysis; acridanes; structure; NADN ELECTRON-TRANSFER; HYDRIDE-TRANSFER; 9-SUBSTITUTED 10-METHYL-9,10-DIHYDROACRIDINES; GLOBAL OPTIMIZATION; RADICAL CATIONS; SYSTEMS; MODEL; BOND

DOI:

10.1007/s10947-008-0002-y

Web of Science ID:

ISI:000255585700002

Соавторы в МНС:

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Другие поля

Поле	Значение
Month	JAN
Publisher	SPRINGER
Address	233 SPRING STREET, NEW YORK, NY 10013 USA
Language	English
Keywords-Plus	ELECTRON-TRANSFER; HYDRIDE-TRANSFER; 9-SUBSTITUTED 10-METHYL-9,10-DIHYDROACRIDINES; GLOBAL OPTIMIZATION; RADICAL CATIONS; SYSTEMS; MODEL; BOND
Research-Areas	Chemistry
Web-of-Science-Categories	Chemistry, Inorganic \& Nuclear; Chemistry, Physical
Author-Email	maria\_grishina@csu.ru
ResearcherID-Numbers	Potemkin, Vladimir/Q-6008-2016 Grishina, Maria/C-6148-2015
ORCID-Numbers	Potemkin, Vladimir/0000-0002-5244-8718 Grishina, Maria/0000-0002-2573-4831
Number-of-Cited-References	21
Usage-Count-Since-2013	3
Journal-ISO	J. Struct. Chem.
Doc-Delivery-Number	296ZW