Remarkable Anionic Axial Ligand Effects of Iron(III) Porphyrin Complexes on the Catalytic Oxygenations of Hydrocarbons by H2O2 and the Formation of Oxoiron(IV) Porphyrin Intermediates by m-Chloroperoxybenzoic Acid
Wonwoo Nam Prof. Dr.
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorMi H. Lim
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorSo-Young Oh
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorJung H. Lee
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorHa J. Lee
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorSeung K. Woo
Department of Chemistry Sogang University Seoul 121-742 (Korea)
Search for more papers by this authorCheal Kim Prof. Dr.
Department of Fine Chemistry Seoul National Polytechnic University Seoul 139-743 (Korea)
Search for more papers by this authorWoonsup Shin Prof. Dr.
Department of Chemistry Sogang University Seoul 121-742 (Korea)
Search for more papers by this authorWonwoo Nam Prof. Dr.
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorMi H. Lim
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorSo-Young Oh
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorJung H. Lee
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorHa J. Lee
Department of Chemistry and Division of Molecular Life Sciences Ewha Womans University, Seoul 120-750 (Korea) Fax: (+82) 2-3277-2384
Search for more papers by this authorSeung K. Woo
Department of Chemistry Sogang University Seoul 121-742 (Korea)
Search for more papers by this authorCheal Kim Prof. Dr.
Department of Fine Chemistry Seoul National Polytechnic University Seoul 139-743 (Korea)
Search for more papers by this authorWoonsup Shin Prof. Dr.
Department of Chemistry Sogang University Seoul 121-742 (Korea)
Search for more papers by this authorThis work was supported by Center for Cell Signaling Research (1999-2-122-002-4), the Korean Research Foundation (KRF-99-042-D00068), and the MOST through the Women's University Research Fund (99-N6-01-01-A-07).
Abstract
A marked influence on the catalytic epoxidation and hydroxylation of hydrocarbons by aqueous 30 % H2O2 in an aprotic solvent and on the formation of oxoiron(IV) porphyrin intermediates in m-chloroperoxybenzoic acid (m-CPBA) reactions in polar solvent is shown by the anionic axial ligands of an electron-deficient iron(III) porphyrin complex [Fe(tpfpp)X] (tpfpp=meso-tetrakis(pentafluorophenyl)porphinato dianion; see scheme).
References
- 1a
J. L. McLain, J. Lee, J. T. Groves in Biomimetic Oxidations Catalyzed by Transition Metal Complexes ( ), Imperial College Press, London, 2000, pp. 91–169;
10.1142/9781848160699_0003 Google Scholar
- 1b Ortiz de Montellano, Cytochrome P450: Structure, Mechanism, and Biochemistry, , Plenum Press, New York, 1995;
- 1c
T. G. Traylor, P. S. Traylor in Active Oxygen in Biochemistry ( ), Chapman & Hall, London, 1995, pp. 84–187;
10.1007/978-94-011-0609-2_3 Google Scholar
- 1d
B. Meunier in Metalloporphyrins Catalyzed Oxidations ( ), Kluwer, Dordrecht, 1994, pp. 1–47.
10.1007/978-94-017-2247-6_1 Google Scholar
- 2 T. G. Traylor, C. Kim, J. L. Richards, F. Xu, C. L. Perrin, J. Am. Chem. Soc. 1995, 117, 3468–3474, and references therein.
- 3a W. Nam, Y. M. Goh, Y. J. Lee, M. H. Lim, C. Kim, Inorg. Chem. 1999, 38, 3238–3240;
- 3b Y. J. Lee, Y. M. Goh, S.-Y. Han, C. Kim, W. Nam., Chem. Lett. 1998, 837–838.
- 4 J. F. Bartoli, P. Battioni, W. R. De Foor, D. Mansuy, J. Chem. Soc. Chem. Commun. 1994, 23–24.
- 5 J. T. Groves, Y. Watanabe, J. Am. Chem. Soc. 1988, 110, 8443–8452.
- 6 R. A. Sheldon, J. K. Kochi, Metal-Catalyzed Oxidations of Organic Compounds, Academic Press, New York, 1981.
- 7 Hydroxylation of alkanes by hydroxyl or alkoxyl radicals by free radical pathways affords equal amounts of alcohol and ketone products:[6] P. A. MacFaul, K. U. Ingold, D. D. M. Wayner, L. Que, Jr., J. Am. Chem. Soc. 1997, 119, 10 594–10 598.
- 8a J. Bernadou, B. Meunier, Chem. Commun. 1998, 2167–2173;
- 8b K. A. Lee, W. Nam, J. Am. Chem. Soc. 1997, 119, 1916–1922;
- 8c J. T. Groves, J. Lee, S. S. Marla, J. Am. Chem. Soc. 1997, 119, 6269–6273.
- 9 Y. M. Goh, W. Nam, Inorg. Chem. 1999, 38, 914–920.
- 10a Reaction conditions: m-CPBA (1.5×10−3 mmol and 3×10−3 mmol for [Fe(tpfpp)Cl] and [Fe(tpfpp)(CF3SO3)] reactions, repectively, diluted in a solvent mixture (50 μL) of CH3CN and CH2Cl2 (1:1)) was introduced into a 0.1-cm UV cell containing [Fe(tpfpp)X] (5×10−4 mmol and 1×10−3 mmol for [Fe(tpfpp)Cl] and [Fe(tpfpp)(CF3SO3)], respectively) in a solvent mixture (0.5 mL) of CH3CN and CH2Cl2 (1:1) at −60 °C. Spectral changes were directly monitored by UV/Vis spectroscopy (Hewlett Packard 8453 spectrophotometer equipped with Optostat variable-temperature liquid-nitrogen cryostat (Oxford Instruments)).
- 10b Further evidence that 2 was formed in the reaction of [Fe(tpfpp)Cl] and m-CPBA was the silent EPR spectra and the appearance of a β-pyrrole hydrogen resonance signal at δ=4.0 at −50 °C.
- 11 H. Fujii, Chem. Lett. 1994, 1491–1494.
- 12 Solvent and axial ligand effects on the formation of 1 and iron(III) porphyrin N-oxide have been observed in the reaction of an electron-rich iron porphyrin complex, [Fe(tmp)X] (tmp=meso-tetramesitylporphinato dianion), with m-CPBA in toluene:[5] E. Bill, X.-Q. Ding, E. L. Bominaar, A. X. Trautwein, H. Winkler, D. Mandon, R. Weiss, A. Gold, K. Jayaraj, W. E. Hatfield, M. L. Kirk, Eur. J. Biochem. 1990, 188, 665–672.
- 13a J. H. Dawson, Science 1988, 240, 433–439;
- 13b N. Suzuki, T. Higuchi, Y. Urano, K. Kikuchi, H. Uekusa, Y. Ohashi, T. Uchida, T. Kitagawa, T. Nagano, J. Am. Chem. Soc. 1999, 121, 11 571–11 572, and references therein;
- 13c T. L. Poulos, J. Biol. Inorg. Chem. 1996, 1, 356–359;
- 13d K. Yamaguchi, Y. Watanabe, I. Morishima, J. Am. Chem. Soc. 1993, 115, 4058–4065.
- 14a
H.-A. Wagenknecht, W.-D. Woggon, Angew. Chem. 1997, 109, 404–407; Angew. Chem. Int. Ed. Engl. 1997, 36, 390–392;
10.1002/ange.19971090425 Google Scholar
- 14b Z. Gross, J. Biol. Inorg. Chem. 1996, 1, 368–371.
- 15a M. Selke, J. S. Valentine, J. Am. Chem. Soc. 1998, 120, 2652–2653;
- 15b M. Selke, M. F. Sisemore, J. S. Valentine, J. Am. Chem. Soc. 1996, 118, 2008–2012.
- 16 K. Czarnecki, S. Nimri, Z. Gross, L. M. Proniewicz, J. R. Kincaid, J. Am. Chem. Soc. 1996, 118, 2929–2935.
- 17 We reported recently that electron-deficient iron(III) porphyrin complexes tend to cleave the O−O bond of hydroperoxides heterolytically in protic solvent systems, whereas O−O bond homolysis predominates in the reactions of electron-rich iron(III) porphyrins with the oxidants: W. Nam, H. J. Han, S.-Y. Oh, Y. J. Lee, J.-H. Choi, S.-Y. Han, C. Kim, S. K. Woo, W. Shin, J. Am. Chem. Soc., in press.