EPR, 1H and 2H NMR, and Reactivity Studies of the Iron-Oxygen Intermediates in Bioinspired Catalyst Systems Full article
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Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X |
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| Output data | Year: 2011, Volume: 50, Number: 12, Pages: 5526-5538 Pages count : 13 DOI: 10.1021/ic200088e | ||||
| Tags | 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 | ||||
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Funding (1)
| 1 | Russian Foundation for Basic Research | 09-03-00087 |
Abstract:
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.
Cite:
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 ANCAN PMID OpenAlex
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 ANCAN PMID OpenAlex
Dates:
| Submitted: | Jan 14, 2011 |
| Published online: | May 20, 2011 |
| Published print: | Jun 20, 2011 |
Identifiers:
| Web of science: | WOS:000291422100030 |
| Scopus: | 2-s2.0-79958806293 |
| Elibrary: | 16988086 |
| Chemical Abstracts: | 2011:638513 |
| Chemical Abstracts (print): | 155:40507 |
| PMID: | 21598909 |
| OpenAlex: | W2316012065 |