Estudio teĆ³rico de la determinaciĆ³n selectiva de cobre mediante el uso de un sensor basado en ferroceno
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2020
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es
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Universidad AndrƩs Bello
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Licencia CC
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Resumen
La bĆŗsqueda de sensores metĆ”licos altamente selectivos es un Ć”rea de gran interĆ©s. Aunque el
((E)-2-[(3-(2-ferrocenil) vinil)-5,5-dimetilciclohex-2-enylidene]malononitrilio) (S) ha sido
reportado como un compuesto altamente selectivo en la determinaciĆ³n de cobre, los aspectos
involucrados en su alta selectividad son aĆŗn desconocidos, por lo tanto en este trabajo se estudiĆ³
de forma teĆ³rica, la interacciĆ³n de dicho compuesto con algunos cationes metĆ”licos (Cu2+, Zn2+
,
Ca2+ y Na
+
), dentro del marco de la TeorĆa de Funcionales de la densidad. La selectividad fue
evaluada por la formaciĆ³n de los complejos entre el compuesto de interĆ©s y los cationes indicados.
Se evaluaron las diferentes posibilidades de interacciĆ³n del ligando con el metal y se compararon
las energĆas de formaciĆ³n de los complejos obtenidos. Adicionalmente, se realizĆ³ un estudio
estructural caracterizando la distancia de interacciĆ³n entre el centro metĆ”lico y la regiĆ³n mĆ”s
prĆ³xima del ligando y estimando la transferencia de carga entre los dos fragmentos involucrados.
Se obtuvieron complejos de diferente Ćndole, donde la mayor selectividad hacia cobre fue
determinada por la interacciĆ³n de cobre con los pares libres del Ć”tomo de NitrĆ³geno del grupo
CN, interacciĆ³n que fue menor o no se encontrĆ³ con el resto de los metales involucrados en el
estudio. En todos los complejos obtenidos el ligando actuĆ³ como dador de densidad electrĆ³nica,
siendo mƔs favorable la transferencia de carga hacia cobre que hacia cinc, calcio y sodio,
respectivamente. Estas evidencias electrĆ³nicas guardan coherencia con parĆ”metros geomĆ©tricos y
energƩticos obtenidos en el presente trabajo.
Unidad de InvestigaciĆ³n (Licenciado en QuĆmica)
The search for highly selective metal sensors is an area of great interest. Although ((E) -2 - [(3- (2- ferrocenyl) vinyl) -5,5-dimethylcyclohex-2-enylidene] malononitrile) (S) has been reported as a highly selective compound in copper determination, the aspects involved in its high selectivity are still unknown, therefore in this work the interaction of said compound with some metal cations (Cu2+, Zn2+, Ca2+ and Na+ ) was studied in a theoretical way, within the framework of the Density Functional Theory. The selectivity was evaluated by the formation of the complexes between the compound of interest and the indicated cations. The different possibilities of interaction of the ligand with the metal were evaluated and the formation energies of the obtained complexes were compared. Additionally, a structural study was carried out characterizing the interaction distance between the metal center and the nearest region of the ligand and estimating the charge transfer between the two fragments involved. Complexes of different kinds were obtained, where the greater selectivity towards copper was determined by the interaction of copper with the free pairs of the nitrogen atom of the CN group, interaction that was less or was not found with the rest of the metals involved in the study. In all the complexes obtained, the ligand acted as an electron density donor, the transfer of charge to copper being more favorable than to zinc, calcium and sodium, respectively. This electronic evidence is consistent with geometric and energetic parameters obtained in this work.
Unidad de InvestigaciĆ³n (Licenciado en QuĆmica)
The search for highly selective metal sensors is an area of great interest. Although ((E) -2 - [(3- (2- ferrocenyl) vinyl) -5,5-dimethylcyclohex-2-enylidene] malononitrile) (S) has been reported as a highly selective compound in copper determination, the aspects involved in its high selectivity are still unknown, therefore in this work the interaction of said compound with some metal cations (Cu2+, Zn2+, Ca2+ and Na+ ) was studied in a theoretical way, within the framework of the Density Functional Theory. The selectivity was evaluated by the formation of the complexes between the compound of interest and the indicated cations. The different possibilities of interaction of the ligand with the metal were evaluated and the formation energies of the obtained complexes were compared. Additionally, a structural study was carried out characterizing the interaction distance between the metal center and the nearest region of the ligand and estimating the charge transfer between the two fragments involved. Complexes of different kinds were obtained, where the greater selectivity towards copper was determined by the interaction of copper with the free pairs of the nitrogen atom of the CN group, interaction that was less or was not found with the rest of the metals involved in the study. In all the complexes obtained, the ligand acted as an electron density donor, the transfer of charge to copper being more favorable than to zinc, calcium and sodium, respectively. This electronic evidence is consistent with geometric and energetic parameters obtained in this work.
Notas
Palabras clave
Cobre, AnƔlisis, Sensores MetƔlicos, Ferroceno