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Abstract:

The new complex trans-[NCRu(py)4(CN)Ru(py)4NO] (PF6)3 (I) was synthesized. In acetonitrile solution, I shows an intense visible band (555 nm, ε = 5800 M-1 cm-1) and other absorptions below 350 nm, associated with dπ → π*py and πpy → π*py transitions. The visible band is presently assigned as a donor-acceptor charge transfer (DACT) transition from the remote Ru(II) to the delocalized {RuII-NO+} moiety. Photoinduced release of NO is observed upon irradiation at the DACT band. Application of the Hush model reveals strong electronic coupling, with HDA = ∼2000 cm-1. The difference between the optical absorption energy and redox potentials for the donor and acceptor sites (RuIII,II, 1.40 V, and NO+/NO, 0.50 V, vs Ag/AgCl, 3 M KCl, respectively) (hν - ΔEred) is 1.33 eV, a large value which probably relates to the significant changes in distances and angles for the Ru-N-O moiety upon reduction. UV-vis absorptions, IR frequencies, and redox potentials are solvent-dependent. Controlled potential reduction (of NO+) and oxidation (of Ru(II) associated with the dicyano-chromophore) of I afford stable species, [NCRuII(py)4(CN)Ru(py)4NO]2+ (Ired) and [NCRuIII(py)4(CN)Ru(py)4NO]4+ (Iox), respectively, which are characterized by UV-vis and IR spectroscopies. Ired shows an EPR spectrum characteristic of {Ru(II)-NO•} complexes. Compound I is electrophilically reactive in aqueous solution above pH 5: values of the equilibrium constant for the reaction [NCRu(py)4(CN)Ru(py)4NO]3++ 2 OH- ⇄ [NCRu(py)4(CN)Ru(py)4NO2]+ + H2O, K = 3.2 ± 1.4 × 1015 M-2, and of the rate constant for the nucleophilic addition of OH-, k = 9.2 ± 0.2 × 103 M-1 s-1(25 °C, I = 1 M), are obtained, with ΔΗ‡ = 90.7 ± 3.8 kJ mol-1 and ΔS‡ = 135 ± 13 J K-1 mol-1. The oxidized complex, Iox, shows an enhanced electrophilic reactivity toward OH-. This addition reaction is followed by irreversible processes, which most probably lead to disproportionation of bound nitrite and other products.

Registro:

Documento: Artículo
Título:Metallonitrosyl fragment as electron acceptor: Intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)4(CN)Ru(py)4NO]3+ Ion
Autor:Roncaroli, F.; Baraldo, L.M.; Slep, L.D.; Olabe, J.A.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Inquimae, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Pabellón 2, Ciudad Universitaria, C1428EHA Buenos Aires, Argentina
Palabras clave:acetonitrile; ion; metal; nitric oxide; nitrite; ruthenium derivative; solvent; aqueous solution; article; chemical reaction; chromatophore; complex formation; electron; electron spin resonance; electronics; energy; equilibrium constant; infrared spectroscopy; irradiation; light absorption; model; oxidation reduction potential; pH; reduction; surface charge; synthesis; ultraviolet radiation
Año:2002
Volumen:41
Número:7
Página de inicio:1930
Página de fin:1939
DOI: http://dx.doi.org/10.1021/ic0109896
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:acetonitrile, 75-05-8; nitric oxide, 10102-43-9; nitrite, 14797-65-0
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v41_n7_p1930_Roncaroli

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Citas:

---------- APA ----------
Roncaroli, F., Baraldo, L.M., Slep, L.D. & Olabe, J.A. (2002) . Metallonitrosyl fragment as electron acceptor: Intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)4(CN)Ru(py)4NO]3+ Ion. Inorganic Chemistry, 41(7), 1930-1939.
http://dx.doi.org/10.1021/ic0109896
---------- CHICAGO ----------
Roncaroli, F., Baraldo, L.M., Slep, L.D., Olabe, J.A. "Metallonitrosyl fragment as electron acceptor: Intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)4(CN)Ru(py)4NO]3+ Ion" . Inorganic Chemistry 41, no. 7 (2002) : 1930-1939.
http://dx.doi.org/10.1021/ic0109896
---------- MLA ----------
Roncaroli, F., Baraldo, L.M., Slep, L.D., Olabe, J.A. "Metallonitrosyl fragment as electron acceptor: Intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)4(CN)Ru(py)4NO]3+ Ion" . Inorganic Chemistry, vol. 41, no. 7, 2002, pp. 1930-1939.
http://dx.doi.org/10.1021/ic0109896
---------- VANCOUVER ----------
Roncaroli, F., Baraldo, L.M., Slep, L.D., Olabe, J.A. Metallonitrosyl fragment as electron acceptor: Intramolecular charge transfer, long range electronic coupling, and electrophilic reactivity in the trans-[NCRu(py)4(CN)Ru(py)4NO]3+ Ion. Inorg. Chem. 2002;41(7):1930-1939.
http://dx.doi.org/10.1021/ic0109896