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

Fernando Niemevz; Juan M. Lázaro Martínez; Romina Carballo; Irene Rezzano; Graciela Y. Buldain

doi:10.1055/s-2006-926330

PAPER

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

Fernando Niemevz^a, Juan M. Lázaro Martínez^a, Romina Carballo^b, Irene Rezzano^b,1, Graciela Y. Buldain*^a,1
^a Cátedra de Química Orgánica II, Departamento de Química Orgánica, Universidad de Buenos Aires, Junín 956, 1113 Buenos Aires, Argentina
Fax: +54(011)49648250; e-Mail: gbuldain@ffyb.uba.ar;
^b Cátedra de Química Analítica, Departamento de Química Analítica y Fisicoquímica, Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 956, 1113 Buenos Aires, Argentina

Abstract

All articles of this category

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

Full Text

References

1

CONICET permanent staff.

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