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Titolo:
New insights into the mechanisms of O-O bond cleavage of hydrogen peroxideand tert-alkyl hydroperoxides by iron(III) porphyrin complexes
Autore:
Nam, W; Han, HJ; Oh, SY; Lee, YJ; Choi, MH; Han, SY; Kim, C; Woo, SK; Shin, W;
Indirizzi:
Ewha Womans Univ, Dept Chem, Seoul 120750, South Korea Ewha Womans Univ Seoul South Korea 120750 hem, Seoul 120750, South Korea Ewha Womans Univ, Div Mol Life Sci, Seoul 120750, South Korea Ewha Womans Univ Seoul South Korea 120750 Sci, Seoul 120750, South Korea Seoul Natl Polytech Univ, Dept Fine Chem, Seoul 139743, South Korea Seoul Natl Polytech Univ Seoul South Korea 139743 ul 139743, South Korea Sogang Univ, Dept Chem, Seoul 121742, South Korea Sogang Univ Seoul South Korea 121742 ept Chem, Seoul 121742, South Korea
Titolo Testata:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
fascicolo: 36, volume: 122, anno: 2000,
pagine: 8677 - 8684
SICI:
0002-7863(20000913)122:36<8677:NIITMO>2.0.ZU;2-2
Fonte:
ISI
Lingua:
ENG
Soggetto:
STEREOSPECIFIC ALKANE HYDROXYLATION; METHANE MONOOXYGENASE HYDROXYLASE; HEME-CONTAINING OXYGENASES; FREE-RADICAL MECHANISMS; VALENT IRON-PORPHYRIN; BUTYL HYDROPEROXIDE; PROXIMAL LIGAND; AQUEOUS-SOLUTION; COMPOUND-I; TITANIUM(IV)-CATALYZED EPOXIDATION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Life Sciences
Physical, Chemical & Earth Sciences
Citazioni:
89
Recensione:
Indirizzi per estratti:
Indirizzo: Nam, W Ewha Womans Univ, Dept Chem, Seoul 120750, South Korea Ewha Womans Univ Seoul South Korea 120750 oul 120750, South Korea
Citazione:
W. Nam et al., "New insights into the mechanisms of O-O bond cleavage of hydrogen peroxideand tert-alkyl hydroperoxides by iron(III) porphyrin complexes", J AM CHEM S, 122(36), 2000, pp. 8677-8684

Abstract

The mechanisms of heterolytic versus homolytic O-O bond cleavage of H2O2. tert-butyl hydroperoxide (t-BuOOH), 2-methyl-1-phenyl-2-propyl hydroperoxide (MPPH), and m-chloroperoxybenzoic acid (m-CPBA) by iron(III) porphyrin complexes have been studied by carrying out catalytic epoxidations of cyclohexene in protic solvent. In these reactions, various iron(III) porphyrin complexes containing electron-withdrawing and -donating substituents on phenylgroups at the meso position of the porphyrin ring were employed to study the electronic effect of porphyrin ligands on the heterolytic versus homolytic O-O bond cleavage of the hydroperoxides. In addition, various imidazoleswere introduced as axial ligands to investigate the electronic effect of axial ligands on the pathways of hydroperoxide O-O bond cleavage. Unlike theprevious suggestions by Traylor, Bruice, and co-workers, the hydroperoxideO-O bonds were found to be cleaved both heterolytically and homolytically and partitioning between heterolysis and homolysis was significantly affected by the electronic nature of the iron porphyrin complexes (i.e., electronic properties of porphyrin and axial ligands). Electron-deficient iron porphyrin complexes show a tendency to cleave the hydroperoxide O-O bonds heterolytically, whereas electron-rich iron porphyrin complexes cleave the hydroperoxide O-O bonds homolytically. The heterolytic versus homolytic O-O bondcleavage of the hydroperoxides was also found to be significantly affectedby the substituent of the hydroperoxides, ROOH (R = C(O)R', H, C(CH3)(3), and C(CH3)(2)CH2Ph for m-CPBA, H2O2, t-BuOOH, and MPPH, respectively), in which the tendency of O-O bond heterolysis was in the order of m-CPBA > H2O2> t-BuOOH > MPPH. This result indicates that the O-O bond of hydroperoxides containing electron-donating tert-alkyl groups such as t-BuOOH and MPPH tends to be cleaved homolytically, whereas electron-withdrawing substituentssuch as an acyl group in m-CPBA facilitates O-O bond heterolysis. Since wehave observed that the homolytic O-O bond cleavage of hydroperoxides prevails in the reactions performed with electron-rich iron porphyrin complexes and with hydroperoxides containing electron-donating substituents such as the tert-alkyl group, we suggest that the homolytic O-O bond cleavage is facilitated when more electron density resides on the O-O bond of (Porp)Fe(III)-OOR intermediates. We also present convincing evidence that the previous assertion that the reactions of iron(III) porphyrin complexes with hydrogenperoxide and tert-alkyl hydroperoxides invariably proceed by heterolytic O-O bond cleavage in protic solvent and that the failure to obtain high epoxide yields in iron porphyrin complex-catalyzed epoxidation of olefins by hydroperoxides is due to the mechanism of heterolytic O-O bond cleavage followed by a fast hydroperoxide oxidation is highly unlike.

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Documento generato il 02/04/20 alle ore 22:18:30