Journal
INORGANIC CHEMISTRY
Volume 50, Issue 21, Pages 11134-11142Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ic201686c
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Funding
- SOLAR-H2 [EU 212508]
- MICINN [CTQ2010-21497, CSD2006-0003]
- Generalitat de Catalunya [CIRIT/2009 SGR 69]
- Deutsche Forschungsgemeinschaft [Ha3265/3-1]
- U.S. National Science Foundation [CHE09-52054]
- Swedish Energy Agenc
- K&A Wallenberg Foundation
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0952054] Funding Source: National Science Foundation
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The geometry and electronic structure of cis-[Ru-II(bpy)(2)(H2O)(2)](2+) and its higher oxidation state species up formally to Ru-VI have been studied by means of UV-vis, EPR, XAS, and DFT and CASSCF/CASPT2 calculations. DFT calculations of the molecular structures of these species show that, as the oxidation state increases, the Ru-O bond distance decreases, indicating increased degrees of Ru-O multiple bonding. In addition, the O-Ru-O valence bond angle increases as the oxidation state increases. EPR spectroscopy and quantum chemical calculations indicate that low-spin configurations are favored for all oxidation states. Thus, cis-[Ru-IV(bpy)(2)(OH)(0)](2+) (d(4)) has a singlet ground state and is EPR-silent at low temperatures, while cis-[Ru-V(bpy)(2)(O)(OH)](2+) (d(3)) has a doublet ground state. XAS spectroscopy of higher oxidation state species and DFT calculations further illuminate the electronic structures of these complexes, particularly with respect to the covalent character of the O-Ru-O fragment. In addition, the photochemical isomerization of cis-[Ru-II(bpy)(2)(H2O)(2)](2+) to its trans-[Ru-II(bpy)(2)(H2O)(2)](2+) isomer has been fully characterized through quantum chemical calculations. The excited-state process is predicted to involve decoordination of one aqua ligand, which leads to a coordinatively unsaturated complex that undergoes structural rearrangement followed by recoordination of water to yield the trans isomer.
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