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Abstract:

The (2,2′-bipyrazine)ruthenium(II)- and (2,2′-bipyridine)osmium(II)-tetracyanide complexes were prepared as sodium and potassium salts, respectively. Assignments of the MLCT (dπ(M) →- p(L-L)) and IL (π(L-L) → π(L-L)) bands were performed analyzing spectra in aqueous solution and in organic solvents. Upon changing the solvent, we detected strong solvatochromic shifts, the energies of the MLCT bands going to lower values when the Lewis acidity of the solvent (measured by the Gutmann’s acceptor number) was decreased. Redox potential values for the Ru(III,II) and Os(III,II) couples were also solvent-dependent, decreasing with the decrease in acceptor number. The basicities of coordinated cyanides toward the proton were measured through spectrophotometric titrations; the pKa values so obtained, together with the IR measurements in the C-N stretching region (in solid samples and in organic solvents), and the potentials for ligand (L-L) reduction (in dimethylformamide solutions) were used as additional indicators of the s-p bonding interactions. Bipyrazine behaves as a stronger p-acceptor than bipyridine for a given metal center. On the other hand, for the same ligand environment, the Os(II) metal center behaves as a stronger p-donor compared to ruthenium and iron. The p-acceptor ability of the chelating ligand is enhanced in weakly acceptor solvents, associated with the changes in specific cyanide-solvent interactions. The complexes emit poorly in aqueous solutions at room temperature, with low quantum yields, as predicted by the potentials of the M(III,II) couples. The excited states are very strong reductants, as well as very weak oxidants. © 1995, American Chemical Society. All rights reserved.

Registro:

Documento: Artículo
Título:Comparative Bonding and Photophysical Properties of 2,2′-Bipyridine and 2,2′-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium
Autor:Posse, M.E.G.; Katz, N.E.; Baraldo, L.M.; Polonuer, D.D.; Colombano, C.G.; Olabe, J.A.
Filiación:Instituto de Química Física, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 491, 4000 S. M. de Tucumán, Argentina
Departamento de Química Inorgánica, Analítica y Química Física, Inquimae, Universidad de Buenos Aires, 1428 Capital Federal, Argentina
Año:1995
Volumen:34
Número:7
Página de inicio:1830
Página de fin:1835
DOI: http://dx.doi.org/10.1021/ic00111a034
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v34_n7_p1830_Posse

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Citas:

---------- APA ----------
Posse, M.E.G., Katz, N.E., Baraldo, L.M., Polonuer, D.D., Colombano, C.G. & Olabe, J.A. (1995) . Comparative Bonding and Photophysical Properties of 2,2′-Bipyridine and 2,2′-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium. Inorganic Chemistry, 34(7), 1830-1835.
http://dx.doi.org/10.1021/ic00111a034
---------- CHICAGO ----------
Posse, M.E.G., Katz, N.E., Baraldo, L.M., Polonuer, D.D., Colombano, C.G., Olabe, J.A. "Comparative Bonding and Photophysical Properties of 2,2′-Bipyridine and 2,2′-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium" . Inorganic Chemistry 34, no. 7 (1995) : 1830-1835.
http://dx.doi.org/10.1021/ic00111a034
---------- MLA ----------
Posse, M.E.G., Katz, N.E., Baraldo, L.M., Polonuer, D.D., Colombano, C.G., Olabe, J.A. "Comparative Bonding and Photophysical Properties of 2,2′-Bipyridine and 2,2′-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium" . Inorganic Chemistry, vol. 34, no. 7, 1995, pp. 1830-1835.
http://dx.doi.org/10.1021/ic00111a034
---------- VANCOUVER ----------
Posse, M.E.G., Katz, N.E., Baraldo, L.M., Polonuer, D.D., Colombano, C.G., Olabe, J.A. Comparative Bonding and Photophysical Properties of 2,2′-Bipyridine and 2,2′-Bipyrazine in Tetracyano Complexes Containing Ruthenium and Osmium. Inorg. Chem. 1995;34(7):1830-1835.
http://dx.doi.org/10.1021/ic00111a034