Trinuclear Pyrazine-Bridged Ruthenium Complexes: Syntheses, Electrochemistry, NIR−Vis Spectra, and Their Interpretation in Terms of a 5-Orbital−3-Parameter Model
- 14 February 2002
- journal article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 41 (5), 1263-1271
- https://doi.org/10.1021/ic010869y
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+.Keywords
This publication has 72 references indexed in Scilit:
- M(μ-CN)Fe(μ-CN)M‘ Chains with Phthalocyanine Iron Centers: Redox, Spin-State, and Mixed-Valence PropertiesInorganic Chemistry, 2000
- The FeIII/FeIIvs Fe22.5Formulation in Mixed-Valent Species [(NC)4Fe(BL)Fe(CN)4]3-, BL = 2,2‘-Bipyrimidine and 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine. Distance and Size Do Not Always MatterInorganic Chemistry, 1999
- Linear and Bent M(μ-CN)Pt(μ-CN)M Chains: Probes for Remote Metal−Metal InteractionsInorganic Chemistry, 1999
- Solvent effect on the optical properties of [(NH3)5Ru–pyrazine]+m (m=2,3) complexes by ab initio calculationsThe Journal of Chemical Physics, 1998
- Metal−Ligand Coupling Elements and Antiferromagnetic Superexchange in Ruthenium DimersInorganic Chemistry, 1998
- Mixed-Valence Cyanopyridine-Bridged Complexes of Pentacyanoferrate and Pentaammineruthenium: Electronic Structure, Stability, and Redox ReactivityInorganic Chemistry, 1996
- Electron transfer and energy transfer through bridged systems. 5. Intermetallic coupling and electronic spectra of the bis(pentaammineruthenium) complexes of .alpha.,.omega.-dipyridyl trans-polyenes in nitrobenzeneInorganic Chemistry, 1990
- A model for the optical absorption spectrum of (.mu.-pyrazine) decaamminediruthenium(5+): What hath Creutz and Taube wrought?Journal of the American Chemical Society, 1987
- Vibronic coupling model for calculation of mixed valence absorption profilesJournal of the American Chemical Society, 1978
- Synthesis and properties of pentaamminepyridineruthenium(II) and related pentaammineruthenium complexes of aromatic nitrogen heterocyclesJournal of the American Chemical Society, 1968