The Active Intermediates of Non-Heme-Iron-Based Systems for Catalytic Alkene Epoxidation with H2O2/CH3COOH Full article
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European Journal of Inorganic Chemistry
ISSN: 1434-1948 , E-ISSN: 1099-0682 |
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| Output data | Year: 2007, Number: 6, Pages: 852-857 Pages count : 6 DOI: 10.1002/ejic.200600895 | ||
| Tags | Acylperoxido complexes, EPR spectroscopy, Intermediates, NMR spectroscopy, Oxidation, Oxidoiron(IV) complexes, Paramagnetic | ||
| Authors |
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| Affiliations |
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Funding (1)
| 1 | Russian Foundation for Basic Research | 06-03-32214 |
Abstract:
Iron complexes with aminopyridine ligands [FeII(BPMEN)(CH3CN)2](ClO4)2 (1) [BPMEN = N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-diaminoethane] and [FeII(TPA)(CH3CN)2](ClO4)2 (2) [TPA = tris(2-pyridylmethyl)amine] are rare examples of iron-based catalysts for selective olefin epoxidation with H2O2/CH3COOH combination. Using 1,2H NMR and EPR spectroscopy, it was shown that the active species of the catalytic systems 1/H2O2/CH3COOH and 2/H2O2/CH3COOH are mononuclear iron(IV)-oxido complexes [(BPMEN)FeIV=O(S)]2+ and [(TPA)FeIV=O(S)]2+, respectively (S = solvent molecule). These intermediates are formed via decomposition of the corresponding acylperoxido complexes [(L)FeIII(O3CCH3)]2+ (L = BPMEN or TPA). The acylperoxido complex [(BPMEN)FeIII(O3CCD3)]2+ was identified in the catalytic system 1/H2O2/CD3COOD by 2H NMR spectroscopy. The improved epoxidation activity and selectivity of the catalytic systems 1/H2O2/CH3COOH and 2/H2O2/CH3COOH, with respect to 1/H2O2 and 2/H2O2, is caused by the effective formation of intermediates [(L)FeIV=O(S)]2+ via decomposition of the acylperoxido complexes [(L)FeIII(O3CCH3)]2+.
Cite:
Duban E.A.
, Bryliakov K.P.
, Talsi E.P.
The Active Intermediates of Non-Heme-Iron-Based Systems for Catalytic Alkene Epoxidation with H2O2/CH3COOH
European Journal of Inorganic Chemistry. 2007. N6. P.852-857. DOI: 10.1002/ejic.200600895 WOS Scopus РИНЦ ANCAN OpenAlex
The Active Intermediates of Non-Heme-Iron-Based Systems for Catalytic Alkene Epoxidation with H2O2/CH3COOH
European Journal of Inorganic Chemistry. 2007. N6. P.852-857. DOI: 10.1002/ejic.200600895 WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
| Submitted: | Sep 25, 2006 |
| Published online: | Jan 15, 2007 |
| Published print: | Feb 1, 2007 |
Identifiers:
| Web of science: | WOS:000244906200008 |
| Scopus: | 2-s2.0-34250710008 |
| Elibrary: | 13564075 |
| Chemical Abstracts: | 2007:325235 |
| Chemical Abstracts (print): | 148:144333 |
| OpenAlex: | W2040924564 |