Structure and Properties of Tungsten Peroxopolyoxo Complexes – Promising Catalysts for Organics Oxidation. II: Cation Type Influence on the Tungsten Peroxocomplex Structure
Научная публикация
| Общее |
Язык:
Английский,
Жанр:
Статья (Full article),
Статус опубликования:
Опубликована,
Оригинальность:
Оригинальная
|
| Журнал |
Journal of Molecular Catalysis A: Chemical
ISSN: 1381-1169
|
| Вых. Данные |
Год: 2013,
Том: 366,
Страницы: 341-346
Страниц
: 6
DOI:
10.1016/j.molcata.2012.10.013
|
| Ключевые слова |
EXAFS and Raman scattering spectroscopy, Metal complex catalysis, Oxotungstates, Peroxopolyoxotungstates, Peucedanin oxidation |
| Авторы |
Kochubey Dimitry I.
1
,
Berdnikova Polina V.
1
,
Pai Zinaida P.
1
,
Chesalov Yuriy A.
1
,
Kanazhevskiy Vladislav V.
1
,
Khlebnikova Tatiana B.
1
|
| Организации |
| 1 |
Институт катализа им. Г.К. Борескова СО РАН
|
|
Информация о финансировании (3)
|
1
|
Российский фонд фундаментальных исследований
|
12-03-00173
|
|
2
|
Министерство образования и науки Российской Федерации
|
14.518.11.7022
|
|
3
|
Президиум РАН
|
5.7.3
|
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.