Mössbauer study of a tetrakis (pentafluorophenyl) porphyrin iron (III) chloride in comparison with the fluorine unsubstituted analogue

Kaczmarzyk, Tomasz; Dziedzic-Kocurek, Katarzyna; Rutkowska, Iwona; Dziliński, Kazimierz

doi:10.1515/nuka-2015-0013

Abstract

Mössbauer investigations, in association with density functional theory (DFT) calculations, have been conducted for the molecular and electronic structures of iron (III) [tetrakis (pentafluorophenyl)] porphyrin chloride [(F₂₀TPP)Fe:Cl], as a Fe(III)-tetraphenylporphyrin complex containing chloride axial ligand and substituted hydrogen atoms by fluorine ones in the four phenyl rings, in comparison with its fluorine unsubstituted analogue [(TPP)Fe:Cl]. It was found that the parameters of Mössbauer spectra of both complexes are close to one another, and correspond to the high-spin state of Fe(III) ions, but they show the different temperature dependence and the quadrupole doublets in Mössbauer spectra show different asymmetry at low temperatures. Results of DFT calculations are analyzed in the light of catalytic activity of the halogenated complex.

References

1. Sheldon, R. A. (1994). Metalloporphyrins in catalytic oxidations. New York: Marcel Dekker.
Search in Google Scholar
2. Meunier, B. (1999). Biomimetic oxidations catalyzed by transition metal complexes. London: Imperial College Press.
Search in Google Scholar
3. Gray, H. B., & Winkler, J. R. (2003). Heme protein dynamics: Electron tunneling and redox triggered folding. In K. M. Kadish, K. M. Smith & G. Guilard (Eds.), The porphyrin handbook (Vol. 11, pp. 51–75). Amsterdam: Academic Press.
Search in Google Scholar
4. Malinowski, T. (2000). Porphyrin-based electrochemical sensors. In K. M. Kadish, K. M. Smith & G. Guilard (Eds.), The porphyrin handbook (Vol. 6, pp. 231–256). San Diego: Academic Press.
Search in Google Scholar
5. Dziedzic-Kocurek, K., Okła, D., & Stanek, J. (2013). Inter- and intramolecular dynamics of iron porphyrins. Nukleonika, 58, 7–11.
Search in Google Scholar
6. Hu, Ch., Noll, B. C., Schultz, C. E., & Scheidt, W. R. (2007). Four-coordinate iron (II) porphyrinates: Electronic configuration change by intermolecular interaction. Inorg. Chem., 46, 619–621. DOI: 10.1021/ic0620182.10.1021/ic0620182
Search in Google Scholar
7. Hoard, J. L., Cohen, G. H., & Glick, M. D. (1967). The stereochemistry of the coordination group in an iron (III) derivative of tetraphenylporphine. J. Am. Chem. Soc., 89, 1992–1996. DOI: 10.1021/ja00985a004.10.1021/ja00985a004
Search in Google Scholar
8. Lang, G., Spartalian, K., Reed, C. A., & Collman, J. P. (1978). Mössbauer effect study of the magnetic properties of S=1 ferrous tetraphenylporphyrin. J. Chem. Phys., 69, 5424–5427. DOI: 10.1063/1.436532.10.1063/1.436532
Search in Google Scholar
9. Wei, L., She, Y., Yu, Y., Yao, X., & Zhang, S. (2012). Substituent effects on geometric and electronic properties of iron tetraphenylporphyrin: A DFT investigation. J. Mol. Model., 18, 2483–2491. DOI: 10.1007/s00894-011-1279-x.10.1007/s00894-011-1279-x
Search in Google Scholar
10. Asghari-Khiavi, M., & Safinejad, F. (2010). Theoretical studies on metal porphyrin halides: Geometrical parameters and nonlinear optical responses. J. Mol. Model., 16, 499–503. DOI: 10.1007/s00894-009-0556-4.10.1007/s00894-009-0556-4
Search in Google Scholar
11. Liu, N., Jiang, G. F., Guo, C. C., & Tan, Z. (2009). Quantitative structure-activity relationship studies on ironporphyrin–catalyzed cyclohexane oxidation with PhIO. J. Mol. Catal. A-Chem., 304, 40–46. DOI: 10.1016/j.molcata.2009.01.021.10.1016/j.molcata.2009.01.021
Search in Google Scholar
12. Lu, Q. Z., Yu, R. Q., & Shen, G. L. (2003). The structure, catalytic activity and reaction mechanism modeling for halogenated iron-tetraphenylporphyrin complexes. J. Mol. Catal. A-Chem., 198, 9–22. DOI: 10.1016/S1381-1169(02)00726-4.10.1016/S1381-1169(02)00726-4
Search in Google Scholar
13. Stephenson, N. A., & Bell, A. T. (2006). Effects of methanol on the therodynamics of iron(III) [tetrakis (pentafluorophenyl)] porphyrin chloride dissociation and the creation of catalytically active species for the epoxidation of cyclooctene. Inorg. Chem., 45, 5591–5599. DOI: 10.1021/ic0521067.10.1021/ic052106716813423
Search in Google Scholar
14. Stephenson, N. A., & Bell, A. T. (2006). A study of the mechanism and kinetics of cyclooctene epoxidation catalyzed by iron (III) tetrakispentafluorophenyl porphyrin. J. Am. Chem. Soc., 127, 8635–8643. DOI: 10.1021/ja043380n.10.1021/ja043380n15954768
Search in Google Scholar
15. Cunningham, I. D., Basaleh, A., & Gazzaz, H. (2012). Pre-steady state reactivity of 5,10,15,20-tetrakis (pentafluorophenyl)-21H, 23H-porphyrin iron (III) chloride with hydrogen peroxide. Dalton Trans., 41, 9158–9160. DOI: 10.1039/c2dt31107k.10.1039/c2dt31107k22735106
Search in Google Scholar
16. Kaczmarzyk, T., Jackowski, T., & Dziliński, K. (2007). Spectroscopic characteristics of Fe^I-phthalocyanine. Nukleonika, 52, 99–103.
Search in Google Scholar
17. Velde, G. Te., Bickelhaupt, F. M., van Gisbergen, S. J. A., Fonseca Guerra, C., Baerends, E. J., Snijders, J. G., & Ziegler, T. (2001). Chemistry with ADF. J. Comput. Chem., 22, 931. DOI: 10.1002/jcc.1056.10.1002/jcc.1056
Search in Google Scholar
18. van Lenthe, E., & Baerends, E. J. (2003). Optimized slater-type basis sets for the elements 1-118. J. Comput. Chem., 24, 1142–1156. DOI: 10.1002/jcc.10255.10.1002/jcc.10255
Search in Google Scholar
19. Scheidt, W. R., & Finnegan, M. G. (1989). Structure of monoclinic chloro (meso-tetraphenylporphyrinato) iron(III). Acta Crystallogr. Sect. C-Cryst. Struct. Commun., 45, 1214–1216. DOI: 10.S0108270189000715.10.1107/S0108270189000715
Search in Google Scholar
20. Scheidt, W. R., & Lee, Y. J. (1987). Recent advances in the stereochemistry of metallotetrapyrroles. Struct. Bond., 64, 1–70. DOI: 10.1007/BFb0036789.10.1007/BFb0036789
Search in Google Scholar
21. Lu, Q. Z., Lu, Y., & Wang, J. J. (2006). DFT study of iron tetraphenylporphyrin chloride and iron pentafluorophenylporphyrin chloride. Chinese J. Chem. Phys., 19, 227–232. DOI: 10.1360/cjcp2006.19(3).227.6.10.1360/cjcp2006.19(3).227.6
Search in Google Scholar
22. Debrunner, P. G. (1989). Mössbauer spectroscopy of iron porphyrins. In A. B. P. Lever & H. B. Gray (Eds.), Iron porphyrins. (Part III, pp. 140–234). New York: VCH Publishers.
Search in Google Scholar
23. Shenoy, G. K., Wagner, F. E., & Kalvius, G. M. (1978). The measurement of the isomer shift. In G. K. Shenoy & F. E. Wagner (Eds.), Mössbauer isomer shifts (pp. 49–110). Amsterdam: North-Holland Publishing Co.
Search in Google Scholar
24. Lyons, J. E., Ellis, P. E., & Myers, H. K. (1995). Halogenated metalloporphyrin complexes as catalysts for selective reactions of acyclic alkanes with molecular oxygen. J. Catal., 155, 59–73. DOI: 10.1006/jcat.1995.1188.10.1006/jcat.1995.1188
Search in Google Scholar
25. Zhan, C. G., Nichols, J. A., & Dixon, D. A. (2003). Ionization potential, electron affinity, electronegativity, hardness and electron excitation energy: Molecular properties from density functional theory orbital energy. J. Phys. Chem. A, 107, 4184–4195. DOI: 10.1021/jp0225774.10.1021/jp0225774
Search in Google Scholar
26. Ernst, J., Subramanian, J., & Fuhrhop, J. H. (1977). Magnetic interactions in iron (III) porphyrin chlorides. Z. Naturforsch., 32a, 1129–1136.10.1515/zna-1977-1008
Search in Google Scholar

Mössbauer study of a tetrakis (pentafluorophenyl) porphyrin iron (III) chloride in comparison with the fluorine unsubstituted analogue

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