EPR, 1H and 2H NMR, and Reactivity Studies of the Iron-Oxygen Intermediates in Bioinspired Catalyst Systems | Sciact - CRIS-система Института катализа

EPR, 1H and 2H NMR, and Reactivity Studies of the Iron-Oxygen Intermediates in Bioinspired Catalyst Systems Научная публикация

Журнал

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Вых. Данные

Год: 2011, Том: 50, Номер: 12, Страницы: 5526-5538 Страниц : 13 DOI: 10.1021/ic200088e

Ключевые слова

STEREOSPECIFIC ALKANE HYDROXYLATION; OLEFIN CIS-DIHYDROXYLATION; SPIN FERRIC HYDROPEROXO; C-H OXIDATION; FE-III-OOH; HYDROGEN-PEROXIDE; SPECTROSCOPIC CHARACTERIZATION; ALKYLPEROXO COMPLEXES; IRON(III) COMPLEXES; ALKENE EPOXIDATION

Авторы

Lyakin Oleg Y. ^1,2 , Bryliakov Konstantin P. ^1,2 , Talzi Evgenii P. ^1,2

Организации

1	Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Lavrentieva 5, Novosibirsk 630090, Russian Federation
2	Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090, Russian Federation

Информация о финансировании (1)

Российский фонд фундаментальных исследований

09-03-00087

Complexes [(BPMEN)Fe(II)(CH(3)CN)(2)](ClO(4))(2) (1, BPMEN = N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)-1,2-diaminoethane) and [(TPA)Fe(II)(CH(3)CN)(2)](ClO(4))(2) (2, TPA = tris(2-pyridylmethyl)amine) are among the best nonheme iron-based catalysts for bioinspired oxidation of hydrocarbons. Using EPR and (1)H and (2)H NMR spectroscopy, the iron-oxygen intermediates formed in the catalyst systems 1,2/H(2)O(2); 1,2/H(2)O(2)/CH(3)COOH; 1,2/CH(3)CO(3)H; 1,2/m-CPBA; 1,2/PhIO; 1,2/(t)BuOOH; and 1,2/(t)BuOOH/CH(3)COOH have been studied (m-CPBA is m-chloroperbenzoic acid). The following intermediates have been observed: [(L)Fe(III)(OOR)(S)](2+), [(L)Fe(IV)═O(S)](2+) (L = BPMEN or TPA, R = H or (t)Bu, S = CH(3)CN or H(2)O), and the iron-oxygen species 1c (L = BPMEN) and 2c (L = TPA). It has been shown that 1c and 2c directly react with cyclohexene to yield cyclohexene oxide, whereas [(L)Fe(IV)═O(S)](2+) react with cyclohexene to yield mainly products of allylic oxidation. [(L)Fe(III)(OOR)(S)](2+) are inert in this reaction. The analysis of EPR and reactivity data shows that only those catalyst systems which display EPR spectra of 1c and 2c are able to selectively epoxidize cyclohexene, thus bearing strong evidence in favor of the key role of 1c and 2c in selective epoxidation. 1c and 2c were tentatively assigned to the oxoiron(V) intermediates.

Lyakin O.Y. , Bryliakov K.P. , Talzi E.P.
EPR, 1H and 2H NMR, and Reactivity Studies of the Iron-Oxygen Intermediates in Bioinspired Catalyst Systems
Inorganic Chemistry. 2011. V.50. N12. P.5526-5538. DOI: 10.1021/ic200088e WOS Scopus РИНЦ CAPlusCA PMID OpenAlex

Поступила в редакцию:	14 янв. 2011 г.
Опубликована online:	20 мая 2011 г.
Опубликована в печати:	20 июн. 2011 г.

Web of science:	WOS:000291422100030
Scopus:	2-s2.0-79958806293
РИНЦ:	16988086
Chemical Abstracts:	2011:638513
Chemical Abstracts (print):	155:40507
PMID (PubMed):	21598909
OpenAlex:	W2316012065

БД	Цитирований
Web of science	96
Scopus	102
РИНЦ	99
OpenAlex	98