51V NMR and EPR Study of the Mechanistic Details of Oxidation with VO(O2) (Pic) (H2O)2 Научная публикация
| Журнал |
Journal of Molecular Catalysis
ISSN: 0304-5102 |
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| Вых. Данные | Год: 1994, Том: 92, Номер: 3, Страницы: 245-255 Страниц : 11 DOI: 10.1016/0304-5102(94)00069-7 | ||||
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Реферат:
Using 51V NMR, it was shown that peroxo complex VO(O2) (Pic) (H2O)2 (Pic = picolinic acid) exists in CH3CN, MeOH and H2O in the forms of VO(O2) (Pic) H2O·CH3CN, VO(O2) (Pic) H2O·MeOH and VO(O2) (Pic) (H2O)2, respectively. To elucidate the nature of reactivity of vanadium peroxo complexes Of VO(O2) (Pic) H2O·S family towards hydrocarbons their interactions with spin trap 3,3,5,5-tetramethyl-pyrroline-N-oxide (TMPO) were investigated by EPR. Only the peroxo complex VO(O2) (Pic) H2O·CH3CN was reactive towards the hydrocarbons and the spin trap. This complex can abstract the β-hydrogen atom from TMPO (VV reduces to VIV by this reaction). Such hydrogen atom abstraction was not observed for the other radical species studied (free radicals OH•(HO2•), RO•(RO2•) and superoxo complex Pd3(OAc)5O2•). The latter species form with TMPO a spin adduct by addition to the double bond. The data provide evidence, that the diradical species VIVOO• are active particles of oxidation by VO(O2) (Pic) H2O·CH3CN.
Deactivation of VO(O2) (Pic) H2O·CH3CN upon substitution of CH3CN by stronger σ-donor ligands (e.g., H2O, MeOH, DMF) may be caused by prevention of electron transfer from the peroxo group to the metal to give VIVOO•. Vanadium(V) superoxo complex VV(O2.−) detected by EPR in a solution of VO(O2) (Pic) (H2O)2 in 30% H2O2was inert towards alkenes and spin traps.
Библиографическая ссылка:
Talsi E.P.
, Shalyaev K.V.
51V NMR and EPR Study of the Mechanistic Details of Oxidation with VO(O2) (Pic) (H2O)2
Journal of Molecular Catalysis. 1994. V.92. N3. P.245-255. DOI: 10.1016/0304-5102(94)00069-7 WOS Scopus РИНЦ CAPlusCA OpenAlex Sciact
51V NMR and EPR Study of the Mechanistic Details of Oxidation with VO(O2) (Pic) (H2O)2
Journal of Molecular Catalysis. 1994. V.92. N3. P.245-255. DOI: 10.1016/0304-5102(94)00069-7 WOS Scopus РИНЦ CAPlusCA OpenAlex Sciact
Даты:
| Поступила в редакцию: | 7 мая 1993 г. |
| Принята к публикации: | 21 мар. 1994 г. |
| Опубликована в печати: | 13 сент. 1994 г. |
| Опубликована online: | 2 окт. 2001 г. |
Идентификаторы БД:
| Web of science: | WOS:A1994PG58400003 |
| Scopus: | 2-s2.0-0028495870 |
| РИНЦ: | 31095493 |
| Chemical Abstracts: | 1995:116521 |
| Chemical Abstracts (print): | 122:30829 |
| OpenAlex: | W2002568787 |
| Sciact: | 12876 |