Abstract
The oxidation of organic sulfides and olefins with tetra-n-butylammonium periodate (TBAP) in the presence of Fe(III) and Mn(III) meso-tetraarylporphyrins bearing phenyl, 2-chlorophenyl, 4-chlorophenyl and 4-methoxyphenyl groups at the meso positions and imidazole (ImH) has been studied and compared. With the exception of the metalloporphyrins with 4-methoxyphenyl substituents, the oxidative stability of the iron porphyrins was considerably greater than that of the manganese ones. The stronger π–π interaction between the porphyrin core and the iron center in comparison with the manganese center was suggested to explain the higher oxidative stability of the iron porphyrins. The metalloporphyrins with poor electron-donating substituents, i.e., 2-chlorophenyl and 4-chlorophenyl often provided much lower catalytic activity compared to the other catalysts. The departure of IO3 −, leading to the formation of high valent oxo metal species, seems to be facilitated by the presence of strong electron-donating groups at the meso positions. In this catalytic system, the sulfoxide/sulfone molar ratio is determined by stereoelectronic properties of the substituents attached to the sulfur atom of the organic sulfide and the meso-aryl groups of the metalloporphyrins. Although the iron porphyrins showed significantly higher catalytic activities compared to the manganese counterparts in the oxidation of methyl phenyl sulfide, the catalytic activities were comparable for the oxidation of diallyl sulfide. On the other hand, the oxidation of olefins with TBAP gave different order of catalytic activities for the metalloporphyrins. However, the manganese porphyrins were generally more efficient catalysts compared to the iron one. Also, the iron or manganese porphyrins with more electron-donating meso substituents were found to be more efficient than the other ones. The competitive oxidation of cis- and trans-stilbene provided evidence for the participation of a high valent oxo metal species and a six-coordinate periodato one as the active oxidants, although in the case of MnT(2-Cl)PPOAc and FeT(2-Cl)PPOAc the results are strongly in favor of a high valent oxo metal species as the dominant active oxidant.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13738-014-0549-9/MediaObjects/13738_2014_549_Fig1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs13738-014-0549-9/MediaObjects/13738_2014_549_Fig2_HTML.gif)
Similar content being viewed by others
References
J.E. Bäckvall, Selective Oxidation of Amines and Sulfides chapter in Modern Oxidation Methods, 2nd edn, ed. by J. E. Bäckvall, Chap. 8, pp. 277–313 (Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim, 2010)
E.N. Prilezhaeva, Sulfones and sulfoxides in the total synthesis of biologically active natural compounds. Russ Chem Rev 69, 367 (2000)
S. Patai, Z. Rappoport, Synthesis of sulfones, sulfoxides and cyclic sulfides (John Wiley, Chichester, 1994), pp. 109–254
N.S. Simpkins, Sulfones in organic synthesis (Pergamon Press, Oxford, 1993)
I. Fernandez, N. Khiar, Recent developments in the synthesis and utilization of chiral sulfoxides. Chem Rev 103, 3651 (2003)
A.M. Khenkin, R. Neumann, Oxygen Transfer from sulfoxides: oxidation of alkylarenes catalyzed by a polyoxomolybdate, [PMo12O40]3−. J Am Chem. Soc. 124, 4198 (2002)
B. Meunier, Metalloporphyrins as versatile catalysts for oxidation reaction and oxidative dna cleavage. Chem Rev 92, 1411 (1992)
T.I. Reddy, R.S. Varma, Ti-beta-catalysed selective oxidation of sulfides to sulfoxides using urea–hydrogen peroxide adduct. Chem Commun 5, 471 (1997)
M.H. Ali, G.J.A. Bohnert, Facile and selective procedure for oxidation of sulfides to sulfoxides with molecular bromine on hydrated silica gel in dichloromethane. Synthesis 9, 1238 (1998)
W. Nam, S.Y. Oh, Y.J. Sun, J. Kim, W.K. Kim, S.K. Woo, W. Shin, Factors affecting the catalytic epoxidation of olefins by iron porphyrin complexes and H2O2 in protic solvents. J. Org. Chem. 68, 7903 (2003)
D. Mohajer, M. Abbasi, Solvent effects on catalytic epoxidation of alkenes by Tetra-n-butylammonium periodate and (Tetraarylporphyrinato) manganese(III). Eur. J. Inorg. Chem 20, 3218 (2008)
S. Zakavi, A. Abasi, A. Pourali, S. Talebzadeh, Metalloporphyrin-catalyzed chemoselective oxidation of sulfides with polyvinylpyrrolidone-supported hydrogen peroxide: a simple catalytic system for selective oxidation of sulfides to sulfoxides. Bull. Korean Chem. Soc. 33, 35 (2012)
C. Abebrese, Y. Huang, A. Pan, Z. Yuan, R. Zhang, Kinetic studies of oxygen atom transfer reactions from trans-dioxoruthenium(VI) porphyrins to sulfides. J. Inorg. Biochem. 105, 1555 (2011)
S. Campestrini, U. Tonellato, Manganeseporphyrin-catalysed heterogeneous and unusually chemioselective oxidations of sulfides by monopersulfate in supercritical CO2. J. Mol. Catalysis A: Chem 164, 263 (2000)
V. Mirkhani, M. Moghadam, S. Tangestaninejad, I. Mohammdpoor-Baltork, H. Kargar, M. Araghi, Highly efficient oxidation of sulfides with sodium periodate catalyzed by reusable silica supported Mn(Br8TPP)Cl and Mn(TPP)Cl catalysts under various reaction conditions. Appl. Catal. A 353, 61 (2009)
A. Ghaemi, S. Rayati, S. Zakavi, N. Safari, Highly efficient oxidation of sulfides to sulfones with tetra-n-butylammonium hydrogen monopersulfate catalyzed by β-tri- and tetra-brominated meso-tetraphenylporphyrinatomanganese(III) acetate. Appl. Catal. A 353, 154 (2009)
E. Sansiaume, R. Ricoux, D. Gori, J.-P. Mahy, Oxidation of organic molecules in homogeneous aqueous solution catalyzed by hybrid biocatalysts (based on the Trojan Horse strategy). Tetrahedron Asymmetry 21, 1593 (2010)
A. Rezaeifard, M. Jafarpour, H. Raissi, E. Ghiamati, A. Tootoonchi, Factors affecting the reactivity and selectivity in the oxidation of sulfides with tetra-n-butylammonium peroxomonosulfate catalyzed by Mn(III) porphyrins: significant nitrogen donor effects. Polyhedron 30, 592 (2011)
S. Rayati, S. Zakavi, E. Bohloulbandi, M. Jafarian, M. Rashvand avei, Comparative study of the catalytic activity of a series of β-brominated Mn–porphyrins in the oxidation of olefins and organic sulfides: Better catalytic performance of the partially brominated ones. Polyhedron 34, 102 (2012)
S.M.G. Pires, M.M.Q. Simõesa, I.C.M.S. Santos, S.L.H. Rebelo, M.M. Pereira, M.G.P.M.S. Nevesa, J.A.S. Cavaleiro, Biomimetic oxidation of organosulfur compounds with hydrogen peroxide catalyzed by manganese porphyrins. Appl. Catal. A 439–440, 51 (2012)
D. Mohajer, S. Tangestaninejad, Efficient catalytic epoxidation of alkenes by a manganese porphyrin and periodate in the presence of imidazole. J. Chem. Soc., Chem. Commun. 3, 240 (1993)
D. Mohajer, S. Tangestaninejad, Efficient olefin epoxidation with tetrabutylammonium periodate catalyzed by manganese porphyrin in the presence of imidazole. Tetrahedron Lett. 35, 945 (1994)
D. Mohajer, R. Tayebee, H. Goudarziafshar, Sodium periodate epoxidation of alkenes catalysed by manganese porphyrins. J. Chem. Research (S) 2, 168 (1999)
D. Mohajer, G. Karimipour, M. Bagherzadeh, Reactivity studies of biomimetic catalytic epoxidation of alkenes with tetrabutylammonium periodate in the presence of various manganese porphyrins and nitrogen donors: significant axial ligand π-bonding effects. New J. Chem. 28, 740 (2004)
S. Zakavi, F. Heidarizadi, S. Rayati, Comparative study of catalytic activity of some biomimetic models of cytochrome P450 in oxidation of olefins with tetra-n-butylammonium periodate: electron-rich Mn-porphyrins versus the electron-deficient ones. Inorg. Chem. Commun. 14, 1010 (2011)
S. Zakavi, L. Ebrahimi, Substitution effects on the catalytic activity of Mn(III) porphyrins in epoxidation of alkenes with iodosylbenzene: A comparison between the electron-rich and electron-deficient porphyrins. Polyhedron 30, 1732 (2011)
S. Zakavi, A.G. Mojarrad, S. Rayati, Substituent effects on the catalytic activity of a series of manganese meso-tetra(aryl)porphyrins: (2-, 3-, 4)-Pyridyl, 4-sulfonatophenyl and 3-sulfonato-4-methoxyphenyl groups compared to phenyl and 4-methoxyphenyl ones. J. Mol. Catal. A: Chem. 363–364, 153 (2012)
S. Zakavi, T. Mokary yazdeli, Steroelectronic effects of the meso-substituents on the catalytic performance of iron(III) meso-tetraarylporphyrins: pyridyl and N-methylatedpyridyl groups compared to phenyl, 4-methoxyphenyl and 4-sulfonatophenyl ones. J. Mol. Catal. A: Chem 367, 108 (2013)
A.D. Adler, F.R. Longo, J.D. Finarelli, J. Goldmacher, J. Assour, L. Korsakoff, A Simplified synthesis for msso-tetraphenylporphin. J. Org. Chem. 32, 476 (1967)
R.W.A. Johnstone, M.L.P.G. Nanes, M.M. Pereira, R.W.A. Johnstone, A.M.de.A.R. Gonsalves, A.C. Serra, Improved synthesis of 5,10,15,20-tetrakisaryl- and tetrakis-alkylporphyrins. Heterocycles 43, 1425 (1996)
A.D. Adler, F.R. Longo, F. Kampas, J. Kim, On the preparation of metalloporphyrins. J. Inorg. Nucl. Chem. 32, 2443 (1970)
H. Kobayashi, T. Higuchi, Y. Kaizu, H. Osada, M. Aoki, Electronic spectra of tetraphenylporphyrinatoiron(iii) methoxide. Bull. Chem. Soc. Jpn. 48, 3137 (1975)
J.T. Groves, T.E. Nemo, Aliphatic hydroxylation catalyzed by iron porphyrin complexes. J. Am. Chem. Soc. 105, 6243 (1983)
R.J. Abraham, G.E. Hawkes, M.F. Hudson, K.M. Smith, The nuclear magnetic resonance spectra of porphyrins. Part X. I carbon-13 nuclear magnetic resonance spectra of some meso-tetraarylporphyrins and their metal chelates. J. Chem. Soc. Perkin Trans. 2, 204 (1975)
R.A. Sheldon, J.K. Kochi, Metal-catalyzed oxidation of organic compounds (Academic Press, New York, 1981), pp. 8–57
I.D. Cunningham, T.N. Danks, J.N. Hay, I. Hamerton, S. Gunathilagan, C. Janczak, Stability of various metalloporphyrin catalysts during hydrogen peroxide epoxidation of alkene. J. Mol. Catal. A: Chem. 185, 25 (2002)
R. Koerner, M.M. Olmstead, A. Ozarowski, S.L. Phillips, P.M. Van Calcar, K. Winkler, A.L. Balch, Possible intermediates in biological metalloporphyrin oxidative degradation. Nickel, copper, and cobalt complexes of octaethylformybiliverdin and their conversion to a verdoheme. J. Am. Chem. Soc. 120, 1274 (1998)
M. Gouterman, Spectra of porphyrins. J. Mol. Spectrosc. 6, 138 (1961)
S. Zakavi, R. Omidyan, S. Talebzadeh, Porphine core saddling: effects on the HOMO/LUMO gap and the macrocycle bond lengths and bond angles. Polyhedron 49, 36 (2013)
J.E. Huheey, E.A. Keiter, R.L. Keiter, Inorganic chemistry: principles of structure and reactivity, 4th edn. (HarperCollins College Publishers, New York, 1993), pp. 187–188
C. Elschenbroich, Organometallics, 3rd ed., translated by J. Oliveira and C. Elschenbroich. (Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2006) p. 280
B. Figgis, M.A. Hitchman, Ligand field theory and its applications (Wiley-VCH, New York, 2000), pp. 56–57
S. Zakavi, R. Omidyan, L. Ebrahimi, F. Heidarizadi, Substitution effects on the UV–vis and 1H NMR spectra of the dications of meso and/or β substituted porphyrins with trifluoroacetic acid: electron-deficient porphyrins compared to the electron-rich ones. Inorg. Chem. Commun. 14, 1827 (2011)
P.S. Traylor, D. Dolphin, T.G. Traylor, Sterically protected hemins with electronegative substituents: efficient catalysts for hydroxylation and epoxidation. J. Chem. Soc. Chem. Commun 5, 279 (1984)
A.C. Serra, E.C. Marçalo, M.A.d’A. Rocha Gonsalves, A view on the mechanism of metalloporphyrin degradation in hydrogen peroxide epoxidation reactions. J. Mol. Catal. A: Chem 215, 17 (2004)
R.D. Arasasingham, G.X. He, T.C. Bruice, Mechanism of manganese porphyrin-catalyzed oxidation of alkenes. Role of manganese(IV)-oxo species. J. Am. Chem. Soc. 115, 7985 (1993)
W. Nam, M.H. Lim, H.J. Lee, C. Kim, Evidence for the participation of two distinct reactive intermediates in iron(iii) porphyrin complex-catalyzed epoxidation reactions. J. Am. Chem. Soc. 122, 6641 (2000)
W. Nam, S.W. **, M.H. Lim, J.Y. Ryu, C. Kim, Anionic ligand effect on the nature of epoxidizing intermediates in iron porphyrin complex-catalyzed epoxidation reactions. Inorg. Chem. 41, 3647 (2002)
Acknowledgments
Financial support of this work by the Institute for Advanced Studies in Basic Sciences (IASBS) is acknowledged.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
13738_2014_549_MOESM1_ESM.docx
Supplementary material 1 (DOCX 32 kb) Tables S1-S8 and Table S9 show the results of the oxidation of different olefins and the oxidative degradation of the metalloporphyrins, respectively
Rights and permissions
About this article
Cite this article
Zakavi, S., Kayhomayoon, Z. & Rayati, S. Substrate-dependent order of catalytic activity for a series of Fe(III) and Mn(III) porphyrins in the oxidation of organic sulfides and olefins with periodate. J IRAN CHEM SOC 12, 863–872 (2015). https://doi.org/10.1007/s13738-014-0549-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13738-014-0549-9