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Structure and Properties of Tungsten Peroxopolyoxo Complexes – Promising Catalysts for Organics Oxidation. II: Cation Type Influence on the Tungsten Peroxocomplex Structure Full article

Journal Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169
Output data Year: 2013, Volume: 366, Pages: 341-346 Pages count : 6 DOI: 10.1016/j.molcata.2012.10.013
Tags EXAFS and Raman scattering spectroscopy, Metal complex catalysis, Oxotungstates, Peroxopolyoxotungstates, Peucedanin oxidation
Authors Kochubey Dimitry I. 1 , Berdnikova Polina V. 1 , Pai Zinaida P. 1 , Chesalov Yuriy A. 1 , Kanazhevskiy Vladislav V. 1 , Khlebnikova Tatiana B. 1
Affiliations
1 Boreskov Institute of Catalysis, Siberian Branch of RAS, pr. Lavrentieva 5, 630090 Novosibirsk, Russia

Funding (3)

1 Russian Foundation for Basic Research 12-03-00173
2 The Ministry of Education and Science of the Russian Federation 14.518.11.7022
3 Президиум РАН 5.7.3

Abstract: Catalysis via metal complexes has been studied using EXAFS and Raman spectroscopy. EXAFS studies have shown that in tungsten peroxocomplexes containing quaternary ammonium organic cation substitution affects the structure of anion {PO4[WO(O2)2]4}3−. The last complex in series [Bun4N]3{PO4[WO(O2)2]4}, [C5H5NCet]3{PO4[WO(O2)2]4} and [Et2Bn2N]3{PO4[WO(O2)2]4} demonstrates the most evident structure alteration. Vibration spectroscopy proves that structure conversion is related to the strength reduction of end double bond Wdouble bond; length as m-dashO. As a result, antibate Wsingle bondO bond strength increases. That effect also changes the strength of tungsten bonding to cations. Synthesized catalytic complexes [Bun4N]3{PO4[WO(O2)2]4} and [C5H5NCet]3{PO4[WO(O2)2]4} were tested in peucedanin oxidation by hydrogen peroxide. Oxidative catalytic transformation of above mentioned coumarin was shown to yield 2-hydorxyoreozelon, which is a bioactive compound used in medicine. Complex with cetylpyridinium cation appears to be the most active in this reaction.
Cite: Kochubey D.I. , Berdnikova P.V. , Pai Z.P. , Chesalov Y.A. , Kanazhevskiy V.V. , Khlebnikova T.B.
Structure and Properties of Tungsten Peroxopolyoxo Complexes – Promising Catalysts for Organics Oxidation. II: Cation Type Influence on the Tungsten Peroxocomplex Structure
Journal of Molecular Catalysis A: Chemical. 2013. V.366. P.341-346. DOI: 10.1016/j.molcata.2012.10.013 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Aug 1, 2012
Accepted: Oct 15, 2012
Published online: Oct 23, 2012
Published print: Jan 1, 2013
Identifiers:
Web of science: WOS:000313230200044
Scopus: 2-s2.0-84870244977
Elibrary: 20416058
Chemical Abstracts: 2012:1660088
Chemical Abstracts (print): 158:88448
OpenAlex: W1998763650
Citing:
DB Citing
Web of science 14
Scopus 15
Elibrary 18
OpenAlex 16
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