nueva página del texto (beta)
Inglés (pdf)
Artículo en XML
Referencias del artículo
Traducción automática
Enviar artículo por email
Permalink
Texto completo disponible sólo en PDF.
Servicios Personalizados
Revista
Articulo
Indicadores
-
Citado por SciELO -
Accesos
Links relacionados
-
Similares en
SciELO
Compartir
TIP. Revista especializada en ciencias químico-biológicas
versión impresa ISSN 1405-888X
TIP vol.10 no.1 Ciudad de México jun. 2007
Artículos originales
Electrochemical study of cis-diferrocenylethene derivates
Estudio electroquímico de derivados de cis-diferrocenileteno
1Unidad de Investigación en Genética y Toxicologia Ambiental, Facultad de Estudios Superiores Zaragoza, UNAM. Batalla 5 de mayo s/n Esq. Fuerte de Loreto. Col. Ejército de Oriente, Deleg. Iztapalapa, CP. 09230, México D.F.
2Depto. de Química Inorgánica, Facultad de Química, UNAM. Av. Universidad 3000, Ciudad Universitaria, México, D.F. 04510, México.
*Previously Lena Ruiz-Ramirez.
3Instituto de Química, UNAM. Av. Universidad 3000, Ciudad Universitaria, México, D.F. 04510, México.
Ferrocene derivatives have been used in the synthesis of polymeric materials with thermal resistance and nonlinear optical properties, and in the field of supramolecular electrochemistry as redox switching receptors. For these reasons, during the past few years the electrochemical studies on ferrocenyl derivatives have been growing up. In order to characterize molecules with potential uses in the synthesis of polymeric materials and to understand its electrochemical functioning, this paper presents electrochemical studies on these chemicals: 1) cis-diferrocenylethenes derivates (Isopropyl cis-2,3-Diferrocenylacrylate; 2) cis-2,3-Diferrocenylacrylic Acid; 3) cis-2,3-Diferrocenylacrylohydrazide; 4) cis-2,3-Diferrocenylacrylic Acid Piperidide; 5) cis-3,4-Diferrocenyl-2-methylbut-3-en-ol, and 6) cis-1,1-Diphehyl-2,3-Diferrocenylprop-2-en-1-ol. All of the chemicals presented two oxidation processes (l-ll), which were thought to be caused by the oxidation of the ferrocene groups, E1/2(l), E1/2(ll), ΔΕ1/2 (ll-l). The comproportionation constant Kcom was calculated. According to this value, it can be proposed that the molecules containing a carbonyl group (1-4) present larger electronic communication compared to molecules with a hydroxy group (5-6). Uv-vis espectra of all compounds in butironitrile solution were obtained. A correlation between Kcom and λ max was also observed.
Key Words: Cis-2,3-diferrocenylacrylates; cis-2,3-diferrocenyl allyl carbinoles; cyclic voltammetry; diferrocene; electrochemistry; ferrocene
Los derivados del Ferroceno han sido empleados en la síntesis de materiales poliméricos con resistencia térmica y con propiedades ópticas no lineales y en el campo de la electroquímica supramolecular como receptores de interruptores redox. Por estas razones los estudios electroquímicos de los derivados ferrocenil se han incrementado en los últimos años. Con la finalidad de caracterizar moléculas con potenciales usos en la síntesis de materiales poliméricos y entender su comportamiento electroquímico, este trabajo presenta estudios electroquímicos de derivados cis-diferroceniletenos (cis-2,3-Diferrocenilacrilato de isopropiio (1), Ácido cis-2,3-Diferrocenilacrílico (2), cis-2,3-Diferrocenilacrilohidrazida (3), Piperidina del Ácido cis-2,3-Diferrocenilacrílico (4), cis-3,4-Diferrocenil-2-metilbut-3-en-ol (5), cis-1,1-Difenil-2,3-Diferrocenilprop-2-en-1-01 (6). Todos los compuestos presentan dos procesos de oxidación (l-ll), atribuidos a la oxidación de los dos ferrocenos , E1/2(l), E1/2(ll), ΔΕ1/2 (ll-l). Se calcula la constante de desproporción Kcom. De este valor se propone que las moléculas que contienen el grupo carbonilo (1-4) presentan una gran comunicación electronica comparada con las moléculas que contiene un grupo hidroxil (5-6). El espectro UV-vis de todos los compuestos se obtuvo en butironitrilo. Se encontró también una correlación entre Kcom y λ max .
Palabras Clave: Cis-2,3-diferrocenilacrilato; cis-2,3-diferrocenil alilo carbinoles; voltametría cíclica; diferrocenos; electroquímica; ferroceno
References and notes
1. Scott, A.F. Survey of Progress in Chemistry (Academic Press, New York, 1963) Vol. 1, p. 133. [ Links ]
2. Neuse, E.W & Rosenberg, H. Metallocene Polymers (Marcel Dekker, Inc., New York, 1970). [ Links ]
3. Mitchell, J.B.A. Smoke reduction from burning crude oil using ferrocene and its derivatives. Combust Flame 86, 179-184 (1991). [ Links ]
4. Bonczyk, P.A. Effect of Ferrocene on soot in a prevaporized iso-octane/air diffusion flame. Combust Flame 87,233-244.(1991). [ Links ]
5. Somasundaram, G. & Sunavala, P.D. Suppression of soot in the combustion of residual furnace oil using organometallic additives. Fuel 68, 921-927 (1989). [ Links ]
6. Zhang, J. & Megardis, C. M. Soot Suppression by Ferrocene in Laminar Ethylene/Air Nonpremixed Flames. Combust. Flame 105, 528-540 (1996). [ Links ]
7. Pittman, C.U. The Discovery of Metallocene- and Metallocene-Like Addition Polymers. Journal of Inorganic and Organometallic Polymers and Materials 15, 33-55 (2005). [ Links ]
8. Buchmeiser, M. & Schrock, R.R. Synthesis ofpolyenes that contain metallocenes via the living polymerization of ethynylferrocene and ethynylrutheocene. Macromolecules 28, 6642-6649 (1995). [ Links ]
9. Yang, Y., Xie, Z. & Wu, C. Novel synthesis and characterization of side-chain ferrocene-containing polymers. Macromolecules 35, 3426-3432 (2002). [ Links ]
10. Albagli, D., Bazan, C, Wrighton, M.S. & Schröck, R.R. Well-defined redox-active polymers and block copolymers prepared by living ring-opening methatesis polymerization. J. Am. Chem. Soc. 114, 4150-4158 (1992). [ Links ]
11. Morikita, L., Maruyama, L., Yamamoto, L., Kubota, K. & Katada, M. New type of polymer containing 1,1 -ferrocenediyl unit in λ-conjugated main chain. Preparation and redox behavior. Inorg. Chim. Acta 269, 310-312 (1998). [ Links ]
12. Laine, R.M. Inorganic and Organometallic Polymers with Special Properties (Kluwer Academic Publishers, Dordrecht, The Netherlands, 1992). [ Links ]
13. Najafi-Mohajeri, N, Nelson, G.L. & Benrashid, R. Synthesis and properties of new ferrocene-modified ure thane block coplymers. J. Appl. Polym. Sc. 76, 1847-1856 (2000). [ Links ]
14. Long, N.J. Organometallyc compounds for nonliear optics. Angew. Chem. Int. Ed. Engl. 34, 21-38 (1995). [ Links ]
15. Wright, M.E., Toplikar, E. G., Lackritz, H.S. & Kerney, J.T. Organometallyc Nonlinear optical polymers. Organometallic main-chain, side-chain, and guest-host polymers: A study of their orientation and relaxation using second harmonic generation, Macromolecules 27, 3016-3022 (1994). [ Links ]
16. Lin, Z. Organometallic polymers with ferromagnetic properties. Adv. Mater. 11, 1153-1154 (1999). [ Links ]
17. Ingham, S.L., Khan, M.S., Lewis, J., Long, N.J. & Raithby, P.R. Synthesis and characterisation of monomeric, dimeric and polymeric ferrocenylacetylides. Crystal structure of 1,1'-bis (phenylethynyl) ferrocene. 470, 153-159 (1994) [ Links ]
18. Abd-Alla, M.M., Al-Zohry, M.F., Aly, K.I. & Abd-Wahab, M.M. Arylidene polymers. XVIII. Synthesis and thermal behavior of organometallic arylidene polyesters containing ferrocene derivatives in the main chain. J. Appi. Polym. Sci. 47, 323-329 (1993). [ Links ]
19. Gonsalves, K.E., Zhan-Ru, L. & Rausch, M.D. Ferrocene-Containing Polyamides and Polyureas. J. Am. Chem. Soc. 106, 3862-3863 (1994). [ Links ]
20. Kishore, K., Kannan, P. & Iyanar, K. Synthesis, characterization, and Are retardancy of ferrocene containing polyphosphate esters. J. Polym. Sci. Part. A Polym. Chem. 29, 1039-1044 (1991). [ Links ]
21. Gonsalves, K.E. & Rausch, M.D. Segmented poly(ether ure thane) films containing ferrocene units in the hard segments. J. Polym. Sci. Part A. Polym. Chem. 24, 1599-1607 (1986). [ Links ]
22. Casado, CM., Moran, M., Losada, J. & Cuadrado, I. Siloxane and Organosilicon Dimers, Monomers, and Polymers with Amide-Linked Ferrocenyl Moieties. Synthesis, Characterization, and Redox Properties, Inorg. Chem., 34, 1668-1680 (1995). [ Links ]
23. Casado, CM., et al. Redox-active ferrocenyl dendrimers and polymers in solution and immobilised on electrode surfaces. J. Coord. Chem. Rev. 185-186, 53-80 (1999). [ Links ]
24. Beer, P.D., Gale, P.A. & Chen, GZ. Mechanisms of electrochemical recognition of cations, anions and neutral guest species by redox-active receptor molecules. Coord. Chem. Rev. 185-186, 3-36 (1999). [ Links ]
25. Beer, P.D. & Hayes, E.J. Transition metal and organometallic anion complexation agents. Coord. Chem. Rev. 240,167-189 (2003) . [ Links ]
26. Beer, P.D. & Cadman, J. Electrochemical and optical sensing of anions by transition metal based receptors. Coord. Chem. Rev. 205, 131-155 (2000). [ Links ]
27. Ferguson, G., Glidewell, C., Opromolla, G., Zakaria, C.M. & Zanello, P. The redox behaviour of some bis-ferrocenyl compounds: crystal and molecular structures of diferrocenylmethane and diferrocenylmethanol. J. Organomet. Chem. 517, 183-190 (1996). [ Links ]
28. LeVanda, C, Cowan, D.O., Leitch, C. & Bechgaard, K. Mixed-valence diferrocenylacetylene cation. J. Am. Chem. Soc. 96, 6788-6789 (1974). [ Links ]
29. Robin, M.B. & Day, P. Mixed valence chemistry - A survey and classification. Adv. Inorg. Chem. Radiochem. 10, 247 (1967). [ Links ]
30. Klimova, E.I., et al. 2,3-Diferrocenylcyclopropenone: Synthesis, structure and some chemical and electrochemical properties, Eur. J. Org. Chem. 21, 4265-4272 (2003). [ Links ]
31. Klimova, E.I., et al. Reactions of 2,3-diferrocenylcyclopropenone with methyllitium and phenyllithium. J. Organomet. Chem. 689, 2395-2400 (2004). [ Links ]
32. Gritzner, G & Küta, J. Recommendations on reporting electrode potencials in nonaqueous solvents. Pure Appi. Chem. 4, 461-466 (1984). [ Links ]
33. Bard, A.J. & Faulkner, L.R. Electrochemical Methods, Fundamentals and Applications (John Wiley and Sons, New York, 1980). [ Links ]
34. Zanello, P. Inorganic Electrochemistry, theory, practice and application (The Royal Society of Chemistry, Cambridge, UK, 2003). [ Links ]
35. Bott, A.W. The study of multiple electron-transfer reactions by cyclic voltammetry. Current Separation 16, 61-66 (1997). [ Links ]
36. Sohn, Y.S., Hendrickson, D.N. & Gray, H.B. Electronic structure of metallocenes. J. Am. Chem. Soc. 93, 3603-3612 (1970). [ Links ]
37. Lever, A.P.B. Inorganic Electronic Spectroscophy. 2nd. Edition (Elsevier, New York, 1984). [ Links ]
Received: May 11, 2007; Accepted: June 04, 2007
This is an open-access article distributed under the terms of the Creative Commons Attribution License
