Synthesis and Electrochemical Properties of a Novel Mono-meso-ferrocenyl Porphyrin

Abstract

A synthetic route to mono-meso-ferrocenyl porphyrins using a MacDonald-type 2+2 condensation is described. In this method, the substituted diformyldipyrrylmethane 4 is treated with the dicarboxydipyrrylmethane 6. The 5-ferrocenyldipyrrylmethane was obtained by condensation of benzyl 3-methyl-4-ethylpyrrol-2-carboxylate with ferrocenecarboxaldehyde in the presence of p-toluenesulfonic acid. The unequivocal assignment of all proton resonances in the new porphyrin was achieved by means of a detailed analysis of its H-H NOESY correlations. Interestingly, we noticed that the ferrocenyl group introduces an element of asymmetry in the molecule. The corresponding Co(II) and Ni(II) complexes were also prepared. In cyclic voltammograms of the free base and the Co or Ni complexes all voltammetric peaks disappear after four consecutive scans. This result suggests no film formation in any of them.

Key words

porphyrin synthesis - meso-ferrocenyl porphyrin - electrochemistry

References

• 2 Bruti EM. Gianneto M. Mori G. Seeber R. Electroanalysis  1999,  11:  565 
• 3 Carvalho De Medeiras MA. Cosnier S. Deronzier A. Moutet JC. Inorg. Chem.  1996,  35:  2659 
• 4 Bersellini C. Garofano L. Giannetto M. Lusardi F. Mori G. J. Forensic Sci.  2001,  46:  871 
• 5 Araki K. Lima SDe S. Winnischofer H. An. Acad. Bras. Cienc.  2000,  72:  27 
• 6 Blair TL. Allen JR. Daunert S. Bachas LG. Anal. Chem.  1993,  65:  2155 
• 7 Kliza DM. Meyerhoff ME. Electroanalysis  1992,  4:  841 
• 8 Macor KA. Spiro TG. J. Am. Chem. Soc.  1983,  105:  5601 
• 9 Vago M. Campodall’Orto V. Rezzano I. Forzani E. Calvo EJ. J. Electroanal. Chem.  2004,  566:  177 ; and references cited therein
• 10 Campodall’Orto V. Carballo R. Hurst JA. Rezzano I. Spectrochim. Acta, Part A  2005,  61:  2089 
• 11 Boyd PDW. Burrell AK. Campbell WM. Cocks PA. Gordon KC. Jameson GB. Officer DL. Zhao Z. Chem. Commun. (Cambridge)  1999,  637 
• 12 Kim J. Rhee SW. Na YH. Lee KP. Do Y. Jeoung SC. Bull. Korean Chem. Soc.  2001,  22:  1316 
• 13 Venkatraman S. Prabhuraja V. Mishrar R. Kumar R. Chandrashekar TK. Teng W. Senge KR. Indian J. Chem., Sect A: Inorg., Bio-inorg., Phys., Theor. Anal. Chem.  2003,  42:  2191 
• 14 Bucher C. Deviller CH. Moutet JC. Royal G. Saint-Aman E. New J. Chem.  2004,  28:  1584 
• 15 Wollmann RG. Hendrickson DN. Inorg. Chem.  1977,  16:  3079 
• 16 Li F. Yang K. Tyhonas JS. MacCrum KA. Lindsey JS. Tetrahedron  1997,  53:  12339 
• 17 Rhee SW. Park BB. Do Y. Kim J. Polyhedron  2000,  19:  1961 
• 18 Rhee SW. Na YH. Do Y. Kim J. Inorg. Chim. Acta  2000,  309:  49 
• 19 Gunter MJ. Mander LN. J. Org. Chem.  1981,  46:  4792 
• 20 Osuka A. Nagata T. Kobayashi F. Maruyama K. J. Heterocycl. Chem.  1990,  27:  1657 
• 21 Narayanan SJ. Venkatraman S. Dey SR. Sridevi B. Anand VRG. Chandrashekar TK. Synlett  2000,  1834 
• 22 Bucher C. Devillers CH. Moutet JC. Royal G. Saint-Aman E. Chem. Commun. (Cambridge)  2003,  888 
• 23 Arsenault GP. Bullock F. MacDonald SF. J. Am. Chem. Soc.  1960,  82:  4384 
• 24 Valasinas AL. Frydman B. J. Org. Chem.  1976,  41:  2991 
• 25 Robinsohn AE. Buldain GY. J. Heterocycl. Chem.  1995,  32:  1567 
• 26 Robinsohn AE. Maier M. Buldain G. Heterocycles  2000,  53:  2127 
• 27 Battersby AR. Hodgson GL. Ihara M. McDonald E. Saunders J. J. Chem. Soc., Perkin Trans. 1  1973,  2923 
• 28 Awruch J. Frydman B. Tetrahedron  1986,  42:  4137 
• 29 Clezy PS. Fookes CJR. Liepa AJ. Aust. J. Chem.  1972,  25:  1979 
• 30 Kashem A. Anisuzzaman M. Whistler RL. Carbohydr. Res.  1978,  61:  511 
• 31 Buldain G. Díaz L. Frydman B. J. Org. Chem.  1977,  42:  2957 
• 32 Oediger H. Möller F. Eiter K. Synthesis  1972,  59 

1

CONICET permanent staff.