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Osa Codesido, N.; De Candia, A.G.; Weyhermüller, T.; Olabe, J.A.; Slep, L.D. "An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity" (2012) European Journal of Inorganic Chemistry(27):4301-4309
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Abstract:

The pseudo-octahedral nitrosyl species trans-[Ru(DMAP) 4(NO)(OH)] 2+ [1 2+, DMAP = 4-(dimethylamino)pyridine] was prepared by the reaction between [Ru(DMAP) 5(H 2O)] 2+ and NaNO 2 under mild conditions (room temperature, pH = 6-8), and precipitated with NaBF 4 or NaPF 6. Single-crystal X-ray diffraction data of 1(BF 4) 2·2H 2O point to a {RuNO} 6 electronic configuration of the cation, although there is a significant deviation from the expected linear arrangement of the RuNO moiety (Ru-N-O angle: 169.3°). The remarkably low wavenumber of the NO stretching band (ν NO) of 1832 cm -1 in the solid state corresponds to an electron-rich ligand environment with strong backbonding interactions between d π metal orbitals and π* NO orbitals of the (formal) NO + (nitrosonium) ligand. Consistently, the complex acts as a poor electrophile: it is extremely unreactive toward OH - and toward the stronger nucleophile cysteine. Cyclic voltammetry (CV) experiments show three reduction processes in acetonitrile. The first one at -0.50 V [vs. Ag/AgCl, KCl(s)] is reversible on the CV time scale. Spectroelectrochemical experiments (IR and UV/Vis) suggest that the reduced complex has a {RuNO} 7 configuration. The ν NO wavenumber of 1603 cm -1 agrees with a reduction mostly centered at the nitrosyl ligand. This species appears to be inert toward substitution in the coordination sphere, and the original {RuNO} 6 ion can be quantitatively recovered upon oxidation. In contrast, further reduction of this species is completely irreversible, even on the CV timescale, which is probably due to the lability of the presumably formed nitroxyl (NO -) ligand. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Registro:

Documento: Artículo
Título:An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity
Autor:Osa Codesido, N.; De Candia, A.G.; Weyhermüller, T.; Olabe, J.A.; Slep, L.D.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Ciudad Universitaria, Universidad de Buenos Aires, Pabellón 2, C1428EHA Buenos Aires, Argentina
Max-Planck-Institut für Bioanorganische Chemie, Stiftstr. 34-36, 45470 Mülheim, Germany
Palabras clave:Cyclic voltammetry; Density functional calculations; Electronic structure; Nitrogen oxides; Nitrosyl complexes; Ruthenium
Año:2012
Número:27
Página de inicio:4301
Página de fin:4309
DOI: http://dx.doi.org/10.1002/ejic.201200413
Título revista:European Journal of Inorganic Chemistry
Título revista abreviado:Eur. J. Inorg. Chem.
ISSN:14341948
CODEN:EJICF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14341948_v_n27_p4301_OsaCodesido

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Citas:

---------- APA ----------
Osa Codesido, N., De Candia, A.G., Weyhermüller, T., Olabe, J.A. & Slep, L.D. (2012) . An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity. European Journal of Inorganic Chemistry(27), 4301-4309.
http://dx.doi.org/10.1002/ejic.201200413
---------- CHICAGO ----------
Osa Codesido, N., De Candia, A.G., Weyhermüller, T., Olabe, J.A., Slep, L.D. "An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity" . European Journal of Inorganic Chemistry, no. 27 (2012) : 4301-4309.
http://dx.doi.org/10.1002/ejic.201200413
---------- MLA ----------
Osa Codesido, N., De Candia, A.G., Weyhermüller, T., Olabe, J.A., Slep, L.D. "An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity" . European Journal of Inorganic Chemistry, no. 27, 2012, pp. 4301-4309.
http://dx.doi.org/10.1002/ejic.201200413
---------- VANCOUVER ----------
Osa Codesido, N., De Candia, A.G., Weyhermüller, T., Olabe, J.A., Slep, L.D. An electron-rich {RuNO} 6 complex: Trans-[Ru(DMAP) 4(NO)(OH)] 2+ - Structure and reactivity. Eur. J. Inorg. Chem. 2012(27):4301-4309.
http://dx.doi.org/10.1002/ejic.201200413