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Abstract:

The series of complexes [OsII(CN)5L]n-, with L = pyridine or pyrazine derivatives, were prepared in aqueous solution and, in some cases, as sodium or potassium salts. The main feature in the UV-visible spectra is the appearance of an intense, asymmetric MLCT band, split under spin-orbit coupling. The energies and intensities of the MLCT bands decrease and increase, respectively, with the electron-acceptor ability of L, and strong solvatochromic energy shifts are observed in different organic media. The Os(II) complexes can be oxidized chemically or electrochemically to the Os(III) species; the latter show typical LMCT bands in the visible region, independent of L. The redox potentials for the OsIII.II couples (range 0.6-1.0 V (NHE)), shift positively when L becomes more electron-withdrawing or less basic. Reduction potentials for the bound and free Mepz+ ligand showed similar values, ca. -0.53 V (NHE), for the three [M(CN)5L]n- complexes, suggesting similar back-bonding abilities of Fe, Ru, and Os toward a given L ligand; this is confirmed by the linear plots with unit slope obtained for the energy of the MLCT bands of the [M(CN)5L]n- complexes (M = Fe, Ru) against the values for the [Os(CN)5L]n- complexes. The IR spectra show intense and weak bands at ca. 2050 and 2100 cm-1, associated with equatorial and axial cyanide stretchings, respectively. The dissociation rate constant for pyrazine release from the [Os(CN)5pz]3- ion shows a saturation kinetic behavior, typical of dissociative mechanisms found for the iron and ruthenium analog complexes; the specific dissociation rate constant, k-pz = 2.0 × 10-8 s-1 (25 °C, I = 0.5 M), is about 3 and 4 orders of magnitude slower than the values found for [Ru(CN)5pz]3- and [Fe(CN)5pz]3-, respectively; this is ascribed mainly to the strong σ interaction in the Os-L bond.

Registro:

Documento: Artículo
Título:Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands
Autor:Slep, L.D.; Baraldo, L.M.; Olabe, J.A.
Filiación:Depto. de Quim. Inorgánica, Fac. de Ciencias Exactas y Naturales, Ciudad Universitaria, Pabellón 2, Capital Federal 1428, Argentina
Año:1996
Volumen:35
Número:21
Página de inicio:6327
Página de fin:6333
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n21_p6327_Slep

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Citas:

---------- APA ----------
Slep, L.D., Baraldo, L.M. & Olabe, J.A. (1996) . Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands. Inorganic Chemistry, 35(21), 6327-6333.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n21_p6327_Slep [ ]
---------- CHICAGO ----------
Slep, L.D., Baraldo, L.M., Olabe, J.A. "Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands" . Inorganic Chemistry 35, no. 21 (1996) : 6327-6333.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n21_p6327_Slep [ ]
---------- MLA ----------
Slep, L.D., Baraldo, L.M., Olabe, J.A. "Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands" . Inorganic Chemistry, vol. 35, no. 21, 1996, pp. 6327-6333.
Recuperado de https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n21_p6327_Slep [ ]
---------- VANCOUVER ----------
Slep, L.D., Baraldo, L.M., Olabe, J.A. Synthesis and Electronic Structure of Pentacyanoosmate(II) Complexes with N-Heterocyclic Ligands. Inorg. Chem. 1996;35(21):6327-6333.
Available from: https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v35_n21_p6327_Slep [ ]