A study of absorption spectra in the near-infrared (NIR) and visible (vis) regions of trinuclear Ru complexes containing pyrazine (pyz) as bridging ligand, trans-[{Ru(NH3)5pyz}2Ru(NH3) 4]m+ (m = 6-9), is reported. The spectra were recorded on aqueous solutions containing the described species formed in situ by stoichiometric additions of a standard solution of Ce(SO4)2. They were interpreted in terms of a simple 5-orbital-3-parameter model which includes the effects of d-π* interaction and electronic correlation. The model is shown to account for the observed NIR-vis spectra of the complex ions. The 6+ parent species was synthesized by an improved literature method and fully characterized. The novel 8+ complex was also prepared and characterized. The 9+ ion was established to be slowly reduced by water, with dioxygen formation. Electrochemical (CV and DPV) studies were performed on the trinuclear 6+ complex, as well as on its constituent fragments [Ru(NH3)5(pyz)]2+ and trans-[Ru(NH3)4(pyz)2]2+.
Sommovigo, M., Ferretti, A., Venturi, M., Ceroni, P., Giardi, C., Denti, G. (2002). Trinuclear pyrazine-bridged ruthenium complexes: Syntheses, electrochemistry, NIR-vis spectra, and their interpretation in terms of a 5-orbital-3-parameter model. INORGANIC CHEMISTRY, 41(5), 1263-1271 [10.1021/ic010869y].
Trinuclear pyrazine-bridged ruthenium complexes: Syntheses, electrochemistry, NIR-vis spectra, and their interpretation in terms of a 5-orbital-3-parameter model
Venturi M.;Ceroni P.;Denti G.
2002
Abstract
A study of absorption spectra in the near-infrared (NIR) and visible (vis) regions of trinuclear Ru complexes containing pyrazine (pyz) as bridging ligand, trans-[{Ru(NH3)5pyz}2Ru(NH3) 4]m+ (m = 6-9), is reported. The spectra were recorded on aqueous solutions containing the described species formed in situ by stoichiometric additions of a standard solution of Ce(SO4)2. They were interpreted in terms of a simple 5-orbital-3-parameter model which includes the effects of d-π* interaction and electronic correlation. The model is shown to account for the observed NIR-vis spectra of the complex ions. The 6+ parent species was synthesized by an improved literature method and fully characterized. The novel 8+ complex was also prepared and characterized. The 9+ ion was established to be slowly reduced by water, with dioxygen formation. Electrochemical (CV and DPV) studies were performed on the trinuclear 6+ complex, as well as on its constituent fragments [Ru(NH3)5(pyz)]2+ and trans-[Ru(NH3)4(pyz)2]2+.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
