Structure and Properties of Tungsten Peroxopolyoxo Complexes - Promising Catalysts for Organics Oxidation. I. Structure of Peroxocomplexes Studied During the Stepwise Synthesis of Tetra(diperoxotungsten)phosphate-tetra-n-butyl Ammonium
Научная публикация
| Общая информация |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169
|
| Вых. Данные |
Год: 2010,
Том: 332,
Номер: 1-2,
Страницы: 122-127
Страниц
: 6
DOI:
10.1016/j.molcata.2010.09.007
|
| Ключевые слова |
EXAFS and Raman scattering spectroscopy, Metal complex catalysis, Oxidation of cyclic alkenes and alcohols, Oxotungstates, Peroxopolyoxotungstates |
| Авторы |
Pai Zinaida P.
1
,
Kochubey Dimitry I.
1
,
Berdnikova Polina V.
1
,
Kanazhevskiy Vladislav V.
1
,
Prikhodʹko Irina Yu.
1
,
Chesalov Yuriy A.
1
|
| Организации |
| 1 |
Boreskov Institute of Catalysis, Siberian Branch of RAS
|
|
Информация о финансировании (3)
|
1
|
Президиум РАН
|
5.7.3
|
|
2
|
Российский фонд фундаментальных исследований
|
09-03-12317
|
|
3
|
Российский фонд фундаментальных исследований
|
09-03-00395
|
Catalysis via metal complexes has been studied using EXAFS and Raman spectroscopy. Main polyoxo- and peroxopolyoxocomplexes of tungsten, resulting from the interaction of phosphorus tungsten heteropolyacid with hydrogen peroxide in water solutions, were investigated with regard to their form and structure. Interaction was shown to reduce the nuclearity of forming complexes with respect to their precursor – H3PW12O40. The symmetry of oxygen environment of tungsten was found to change, distances W–W remaining the same. After complex [Bun4N]3{PO4[WO(O2)2]4} is isolated, binuclear anion [W2O3(O2)4(H2O)2]2− stays in the solution. Raman scattering, EXAFS and IR spectroscopy show that isolated peroxocomplex in its crystal state has four nuclei, and most probably retains this structure being dissolved in acetonitrile.
Synthesized catalytic complex [Bun4N]3{PO4[WO(O2)2]4} was tested in oxidation of cyclic alkenes and alcohols with hydrogen peroxide. Complex [Bun4N]3{PO4[WO(O2)2]4} was proved to provide higher yields of mono- and dicarbonic acids in comparison to in situ synthesized catalyst.