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Ramírez, C.L.; Pegoraro, C.N.; Filevich, O.; Bruttomeso, A.; Etchenique, R.; Parise, A.R. "Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes" (2012) Inorganic Chemistry. 51(3):1261-1268
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Abstract:

We describe in this paper the properties of [Ru II/III(bpy) 2ClL] +1/+2 and [Ru II/III(bpy) 2L 2] +2/+3. L = ditolyl-3-pyridylamine (dt3pya) is a redox active ligand related to triarylamines, which is very similar to 3-aminopyridine except for the reversible redox behavior. The monosubstituted complex shows a metal-to-ligand charge-transfer (MLCT) at 502 nm, and reversible waves in acetonitrile at E 0(Ru III/II) = 1.07 V, E 0(L +/0) = 1.46 V (NHE). The disubstituted complex shows an MLCT at 461 nm, a photorelease of dt3pya with quantum yield of 0.11 at 473 nm, and two reversible one-electron overlapped waves at 1.39 V associated with one of the ligands (1.37 V) and Ru III/II (1.41 V). Further oxidation of the second ligand at 1.80 V forms a 2,2′-bipiridine derivative, in an irreversible reaction similar to dimerization of triphenylamine to yield tetraphenylbenzidine. In the dioxidized state, the spectroelectrochemistry of the disubstituted complex shows a ligand-to-ligand charge transfer at 1425 nm, with a transition moment of 1.25 Å and an effective two-state coupling of 1200 cm -1. No charge transfer between ligands was observed when Ru was in a 2+ oxidation state. We propose that a superexchange process would be involved in ligand-metal-ligand charge transfer, when ligands and metals are engaged in complementary π interactions, as in metal-ligand-metal complexes. Best orbital matching occurs when metallic donor fragments are combined with acceptor ligands and vice versa. In our case, Ru III bridge (an acceptor) and two dt3pya (donors, one of them being oxidized) made the complex a Robin-Day Class II system, while the Ru II bridge (a donor, reduced) was not able to couple two dt3pya (also donors, one oxidized). © 2012 American Chemical Society.

Registro:

Documento: Artículo
Título:Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes
Autor:Ramírez, C.L.; Pegoraro, C.N.; Filevich, O.; Bruttomeso, A.; Etchenique, R.; Parise, A.R.
Filiación:Departamento de Química, FCEN-Universidad Nacional de Mar Del Plata, Funes 3350, 7600 Mar del Plata, Argentina
INQUIMAE-Departamento de Química Inorgánica, Analítica y Fisicoquímica, FCEN-Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Departamento de Química Orgánica, FCEN-Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires, Argentina
Año:2012
Volumen:51
Número:3
Página de inicio:1261
Página de fin:1268
DOI: http://dx.doi.org/10.1021/ic200966f
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v51_n3_p1261_Ramirez

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Citas:

---------- APA ----------
Ramírez, C.L., Pegoraro, C.N., Filevich, O., Bruttomeso, A., Etchenique, R. & Parise, A.R. (2012) . Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes. Inorganic Chemistry, 51(3), 1261-1268.
http://dx.doi.org/10.1021/ic200966f
---------- CHICAGO ----------
Ramírez, C.L., Pegoraro, C.N., Filevich, O., Bruttomeso, A., Etchenique, R., Parise, A.R. "Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes" . Inorganic Chemistry 51, no. 3 (2012) : 1261-1268.
http://dx.doi.org/10.1021/ic200966f
---------- MLA ----------
Ramírez, C.L., Pegoraro, C.N., Filevich, O., Bruttomeso, A., Etchenique, R., Parise, A.R. "Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes" . Inorganic Chemistry, vol. 51, no. 3, 2012, pp. 1261-1268.
http://dx.doi.org/10.1021/ic200966f
---------- VANCOUVER ----------
Ramírez, C.L., Pegoraro, C.N., Filevich, O., Bruttomeso, A., Etchenique, R., Parise, A.R. Role of ruthenium oxidation states in ligand-to-ligand charge transfer processes. Inorg. Chem. 2012;51(3):1261-1268.
http://dx.doi.org/10.1021/ic200966f