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TIP. Revista especializada en ciencias químico-biológicas

Print version ISSN 1405-888X

TIP vol.10 n.1 México Jun. 2007

 

Artículos originales

Electrochemical study of cis-diferrocenylethene derivates

Estudio electroquímico de derivados de cis-diferrocenileteno

Luis Ortiz-Frade1  * 

Jorge A. Reyna-Cancino2 

Lena Ruiz-Azuara*  2 

Rafael Moreno-Esparza2 

Marcos Martínez-García3 

Elena Klimova2 

Mario Altamirano1 

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.

Abstract

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

Resumen

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

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Received: May 11, 2007; Accepted: June 04, 2007

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