title: cis,cis-[(bpy)2RuVO]2O4+ catalyzes water oxidation formally via in situ generation of radicaloid RuIV-O*.
abstract: The mechanism of the catalytic oxidation of water by cis,cis-[(bpy)(2)Ru(OH(2))](2)O(4+) to give molecular dioxygen was investigated using Density Functional Theory (DFT). A series of four oxidation and four deprotonation events generate the catalytically competent species cis,cis-[(bpy)(2)Ru(V)O](2)O(4+), which breaks the H-OH bond homolytically at the rate determining transition state to give a hydroperoxo intermediate. Our calculations predict a rate determining activation barrier of 25.9 kcal/mol in solution phase, which is in reasonable agreement with the previously reported experimental estimate of 18.7-23.3 kcal/mol. A number of plausible coupling schemes of the two metal sites including strong coupling, weak ferromagnetic and weak antiferromagnetic coupling have been considered. In addition, both high-spin and low-spin states at each of the Ru(V)-d(3) centers were explored and we found that the high-spin states play an important mechanistic role. Our calculations suggest that cis,cis-[(bpy)(2)Ru(V)O](2)O(4+) performs formally an intramolecular ligand-to-metal charge transfer when reacting with water to formally give a cis,cis-[(bpy)(2)Ru(IV)O*](2)O(4+) complex. We propose that the key characteristic of the diruthenium catalyst that allows it to accomplish the most difficult first two oxidations of the overall four-electron redox reaction is directly associated with this in situ generation of two radicaloid oxo moieties that promote the water splitting reaction. A proton coupled metal-to-metal charge transfer follows to yield a Ru(V)/Ru(III) peroxo/aqua mixed valence complex, which performs the third redox reaction to give the superoxo/aqua complex. Finally, intersystem crossing to a ferromagnetically coupled Ru(IV)/Ru(III) superoxo/aqua species is predicted, which will then promote the last redox event to release triplet dioxygen as the final product. A number of key features of the computed mechanism are explored in detail to derive a conceptual understanding of the catalytic mechanism.
authors.affiliation: Department of Chemistry and School of Informatics, Indiana University, Bloomington, Indiana 47405, USA.
authors.forename: Xiaofan
authors.initials: X
authors.lastname: Yang
authors.forename: Mu-Hyun
authors.initials: MH
authors.lastname: Baik
mesh_terms: D015082:2,2'-Dipyridyl / Q000737:chemistry*; D000465:Algorithms; D002384:Catalysis; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D011522:Protons; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism; D017968:Vanadium Compounds / Q000737:chemistry*; D014867:Water / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011522:Protons; D017968:Vanadium Compounds; D014867:Water; D015082:2,2'-Dipyridyl; D012428:Ruthenium; D010100:Oxygen