The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n Full article
Journal |
Journal of Physical Organic Chemistry
ISSN: 0894-3230 , E-ISSN: 1099-1395 |
||||
---|---|---|---|---|---|
Output data | Year: 2013, Volume: 26, Number: 9, Pages: 724-729 Pages count : 6 DOI: 10.1002/poc.3093 | ||||
Tags | copper, metallorganic, quantum chemistry | ||||
Authors |
|
||||
Affiliations |
|
Funding (2)
1 | Russian Foundation for Basic Research | 10-03-00603 |
2 | Russian Foundation for Basic Research | 12-03-31130 |
Abstract:
The adducts of copper(II) chloride complexes with organic radicals may be intermediates in reactions of halohydrocarbons proceeding via radical mechanism and in catalyzed by chlorocuprates. In this paper, the structure and reactivity of chloroorganocuprates with general formula [CuClnCH3]2−n (n = 0–4) were studied at density functional theory (DFT) level of theory. The comparison of geometric and electronic structures of chloroorganocuprates and corresponding copper(II) chloride complexes with the same number of chlorine atoms indicates the higher Cu oxidation state in [CuClnCH3]2−n. The Natural Bonding Orbital analysis confirms the formation of covalent σ-Cu–C bond in these complexes. The analysis of the PES of the system CuCl42−–CH3• indentifies two local minima, corresponding to CuCH3Cl42− and weak complex CuCl32−···CH3Cl, as well as transition state between them. The calculations evidence the spontaneous character of copper ion reduction with formation of halohydrocarbon by chlorine atom detachment from CuCl42− with high energetic effect.
Cite:
Golubeva E.N.
, Zubanova E.M.
, Zhidomirov G.M.
The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n
Journal of Physical Organic Chemistry. 2013. V.26. N9. P.724-729. DOI: 10.1002/poc.3093 WOS Scopus РИНЦ
The Nature of Cu–C Bond and Copper Oxidation State in Chloroorganocuprates [CuClnCH3]2−n
Journal of Physical Organic Chemistry. 2013. V.26. N9. P.724-729. DOI: 10.1002/poc.3093 WOS Scopus РИНЦ
Dates:
Submitted: | Nov 7, 2012 |
Accepted: | Jan 8, 2013 |
Published online: | Feb 12, 2013 |
Published print: | Sep 1, 2013 |
Identifiers:
Web of science | WOS:000325920900007 |
Scopus | 2-s2.0-84882448653 |
Elibrary | 20458965 |
Chemical Abstracts | 2013:245561 |
Chemical Abstracts (print) | 159:347658 |
OpenAlex | W2492009706 |