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Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies Full article

Общее Language: Английский, Genre: Full article,
Status: Published, Source type: Original
Journal European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682
Output data Year: 2010, Volume: 2010, Number: 33, Pages: 5312-5317 Pages count : 6 DOI: 10.1002/ejic.201000615
Tags Density functional calculations, Epoxidation, Hydrogen peroxide, Polyoxometalates, Titanium
Authors Donoeva Baira G. 1 , Trubitsina Tatiana A. 1 , Antonova Nadya S. 2 , Carbo Jorge J. 2 , Poblet Josep M. 2 , Al-Kadamany Ghada 3 , Kortz Ulrich 3 , Kholdeeva Oxana A. 1
Affiliations
1 Boreskov Institute of Catalysis SB RAS
2 Rovira i Virgili University
3 International University Bremen

Funding (5)

1 Government of Catalonia 2009SGR462
2 Government of Catalonia XRQTC
3 Russian Foundation for Basic Research 09-03-91333
4 Ministry of Economy and Business CTQ2008-06549-C02-01/BQU
5 Ministry of Economy and Business

Abstract: Epoxidation of a range of alkenes with aqueous H2O2 easily proceeds in the presence of the dititanium-containing 19-tungstodiarsenate(III) [Ti2(OH)2As2W19O67(H2O)]8– (1), which contains five-coordinate Ti atoms. The results of product and kinetics studies support a mechanism that involves a reversible interaction between H2O2 and the Ti–OH group of 1 to produce a titanium hydroperoxo complex followed by electrophilic oxygen atom transfer from the hydroperoxo ligand to the alkene substrate in the rate-limiting step. The effect of the alkene substrate nature has been investigated at the DFT level. A clear correlation between the energy of πC=C orbitals in the alkene and the turnover frequency values has been found, thereby indicating that the higher nucleophilicity of the alkene, the higher the reactivity. ONIOM (ONIOM = our own n-layered integrated molecular orbital and molecular mechanics) calculations have been employed to evaluate the role of steric effects of alkene substituents. The calculations show that the steric bulk can play a secondary role and tunes the activity in specific cases such as trans-stilbene.
Cite: Donoeva B.G. , Trubitsina T.A. , Antonova N.S. , Carbo J.J. , Poblet J.M. , Al-Kadamany G. , Kortz U. , Kholdeeva O.A.
Epoxidation of Alkenes with H2O2 Catalyzed by Dititanium-Containing 19-Tungstodiarsenate(III): Experimental and Theoretical Studies
European Journal of Inorganic Chemistry. 2010. V.2010. N33. P.5312-5317. DOI: 10.1002/ejic.201000615 publication_identifier_short.wos_identifier_type publication_identifier_short.scopus_identifier_type publication_identifier_short.rinz_identifier_type
Dates:
Submitted: Jun 2, 2010
Published online: Oct 15, 2010
Published print: Nov 1, 2010
Identifiers:
publication_identifier.wos_identifier_type WOS:000285229800015
publication_identifier.scopus_identifier_type 2-s2.0-78649237658
publication_identifier.rinz_identifier_type 16694044
publication_identifier.accession_number_identifier_type 2010:1415615
publication_identifier.chemical_accession_number_identifier_type 154:109014
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