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Homogeneous and Heterogeneous Catalytic Oxidation of Sulfides by H2O2 over Zinc(ii) Compounds Full article

Journal Dalton Transactions
ISSN: 1477-9226 , E-ISSN: 1477-9234
Output data Year: 2009, Pages: 10481-10485 Pages count : 5 DOI: 10.1039/b914355f
Tags AQUEOUS HYDROGEN-PEROXIDE; SELECTIVE OXIDATION; NITRIC-ACID; ASYMMETRIC OXIDATION; CHIRAL SULFOXIDES; SILICA; SULFONES; COMPLEXES
Authors Nuzhdin Alexey L. 1 , Dybtsev Danil N. 2 , Fedin Vladimir P. 2 , Bukhtiyarova Galina A. 1
Affiliations
1 Boreskov Institute of Catalysis, SB RAS, Novosibirsk, 630090, Russia
2 Nikolaev Institute of Inorganic Chemistry, SB RAS, Novosibirsk, 630090, Russia

Funding (2)

1 Russian Foundation for Basic Research 07-03-91208
2 National Research Foundation of Korea 2008-000-10059-0

Abstract: It has been recently shown that zinc compounds are effective catalysts for the oxidation of alkyl aryl sulfides to the corresponding sulfoxides in the presence of hydrogen peroxide. In this paper, we have investigated homogeneous and heterogeneous catalytic oxidation of sulfides by H2O2 over Zn(NO3)2 x 6 H2O and the metal-organic porous material [Zn2(bdc)(L-lac)(dmf)] x DMF (where H2bdc = p-benzenedicarboxylic acid, H2lac = lactic acid), respectively. The experimental data can be explained by the proposed catalytic cycle which includes the activation of H2O2 via coordination to Zn(II) ions followed by oxygen transfer step. In homogeneous conditions, the presence of a large amounts of H2O2 results in the coordination of two molecules of hydrogen peroxide to Zn(II), so that sulfone is formed via transfer of two oxygen atoms from Zn(H2O)4(H2O2)2(2+) active species. Contrary to the homogeneous system, the use of [Zn2(bdc)(L-lac)(dmf)] x DMF as catalyst does not lead to the formation of sulfone in the initial period of reaction. This is consistent with the proposed catalytic cycle of sulfoxidation as each Zn(II) center in the crystalline framework is able to activate only one H2O2 molecule. Our investigations indicate that the sorption and activation of H2O2 molecules by microporous framework [Zn2(bdc)(L-lac)(dmf)] occur faster than sulfide sorption and oxygen transfer.
Cite: Nuzhdin A.L. , Dybtsev D.N. , Fedin V.P. , Bukhtiyarova G.A.
Homogeneous and Heterogeneous Catalytic Oxidation of Sulfides by H2O2 over Zinc(ii) Compounds
Dalton Transactions. 2009. P.10481-10485. DOI: 10.1039/b914355f WOS Scopus Scopus РИНЦ ANCAN PMID OpenAlex
Dates:
Submitted: Jul 16, 2009
Accepted: Sep 28, 2009
Published online: Nov 2, 2009
Published print: Nov 24, 2009
Identifiers:
Web of science: WOS:000272193900013
Scopus: 2-s2.0-72749097209 | 2-s2.0-85034339064
Elibrary: 45571354
Chemical Abstracts: 2009:1472619
Chemical Abstracts (print): 152:144143
PMID: 20023870
OpenAlex: W2139095036
Citing:
DB Citing
Web of science 29
Scopus 25 2
Elibrary 25
OpenAlex 25
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