The cis-[Ru(II)(bpy)2(H2O)2]2+ water-oxidation catalyst revisited.

@article{Sala2010TheCW,
  title={The cis-[Ru(II)(bpy)2(H2O)2]2+ water-oxidation catalyst revisited.},
  author={X. Sala and M. Z. Ertem and Laura Vigara and T. Todorova and Weizhong Chen and R. C. Rocha and F. Aquilante and C. Cramer and L. Gagliardi and A. Llobet},
  journal={Angewandte Chemie},
  year={2010},
  volume={49 42},
  pages={
          7745-7
        }
}
The only operating mechanism in the oxidation of water to dioxygen catalyzed by the mononuclear cis-[RuII(bpy)2(H2O)2]2+ complex when treated with excess CeIV was unambiguously established. Theoretical calculations together with 18O-labeling experiments (see plot) revealed that it is the nucleophilic attack of water on a Ru=O group. 

Figures, Tables, and Topics from this paper

Effects of a proximal base on water oxidation and proton reduction catalyzed by geometric isomers of [Ru(tpy)(pynap)(OH2)]2+.
TLDR
Investigation of the interaction between a base positioned in the second coordination sphere of a complex and a water ligand in water oxidation reactions using geometric isomers of [Ru(tpy)(pynap)(OH(2))](2+) gave intriguing results. Expand
Mechanistic Analysis of Water Oxidation Catalyst cis-[Ru(bpy)2(H2O)2]2+: Effect of Dimerization
While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In thisExpand
Electronic structure of oxidized complexes derived from cis-[Ru(II)(bpy)2(H2O)2]2+ and its photoisomerization mechanism.
TLDR
DFT calculations of the molecular structures of these species show that, as the oxidation state increases, theRu-O bond distance decreases, indicating increased degrees of Ru-O multiple bonding, and XAS spectroscopy and quantum chemical calculations indicate that low-spin configurations are favored for all oxidation states. Expand
Environmental friendly Fe substitutive of Ru in water oxidation catalysis
Abstract The present study pretends to unravel by means of DFT calculations how the energy profile change replacing the precious Ru by the nonprecious Fe for the Ru-HbppExpand
Catalytic water oxidation by a single site [Ru(Fc-tpy)(bpy)OH2]2+ complex and it’s mechanistic study
Abstract The mononuclear complex [Ru(Fc-tpy)(bpy)Cl]PF6 (Ru-Cl) and its corresponding aqua [Ru(Fc-tpy)(bpy)OH2](PF6)2 (Ru-OH2) complex (Fc-tpy = 4′-(2-ferrocenyl)-2,2′:6′2″-terpyridine) have beenExpand
Basic ancillary ligands promote O-O bond formation in iridium-catalyzed water oxidation: a DFT study.
TLDR
The theoretical insight given by the present study can be useful in the design of more efficient water oxidation catalysts, and may increase by using ligand scaffolds bearing internal bases. Expand
Catalytic four-electron oxidation of water by intramolecular coupling of the oxo ligands of a bis(ruthenium-bipyridine) complex.
TLDR
The first successful identification of the metal-O- O-metal stretching band in the oxidation of water indicates that the oxygen-oxygen bond at the stage prior to the evolution of O(2) is formed through the intramolecular coupling of two Ru-oxo groups derived from the [1](3+) ion. Expand
Spectroscopic analysis of catalytic water oxidation by [Ru(II)(bpy)(tpy)H2O]2+ suggests that Ru(V)═O is not a rate-limiting intermediate.
TLDR
This work analyzes one of the most studied homogeneous single-site Ru catalysts and demonstrates that 95% of the Ru complex in the catalytic steady state is of the form [Ru(IV)(bpy)(tpy)═O](2+), which is the simplest representative of a larger class of water oxidation catalysts with neutral, nitrogen containing heterocycles. Expand
Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.
TLDR
A water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS and an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. Expand
Cerium(IV)-driven oxidation of water catalyzed by mononuclear ruthenium complexes
AbstractThis paper reviews results from study of mononuclear ruthenium complexes capable of catalyzing the oxidation of water to molecular oxygen. These catalysts may be classified into threeExpand
...
1
2
3
4
5
...

References

SHOWING 1-10 OF 17 REFERENCES
Mechanism of water oxidation by single-site ruthenium complex catalysts.
TLDR
The mechanism of Ce(IV) water oxidation catalyzed by Ru(tpy)(bpm)(OH(2))](2+) and related single-site catalysts has been determined by a combination of mixing and stopped-flow experiments with spectrophotometric monitoring. Expand
Synthesis and study of mononuclear ruthenium(II) complexes of sterically hindering diimine chelates. Implications for the catalytic oxidation of water to molecular oxygen
Preparation des complexes bis (diimine) de Ru(II), les chelates etant dimethyl-6,6' bipyridine-2,2' ou dimethyl-2,9 phenanthroline-1,10. Comportement electrochimique
Mechanisms of water oxidation catalyzed by the cis,cis-[(bpy)2Ru(OH2)]2O4+ ion.
TLDR
Repetitive mass spectrometric measurement of the isotopic distribution of O(2) formed in reactions catalyzed by (18)O-labeled catalyst established the existence of two reaction pathways characterized by products containing either one atom each from a ruthenyl O and solvent H( 2)O or both O atoms from solvent molecules. Expand
One site is enough. Catalytic water oxidation by [Ru(tpy)(bpm)(OH2)]2+ and [Ru(tpy)(bpz)(OH2)]2+.
TLDR
Single-site catalytic water oxidation by the monomeric complexes [Ru(tpy)(bpm)(OH2)]2+ and [Ru[Ru( tpy)(bpz)( OH2]2+) by a well-defined mechanism involving RuV═O is reported. Expand
Homogeneous light-driven water oxidation catalyzed by a tetraruthenium complex with all inorganic ligands.
TLDR
A totally homogeneous, molecular, visible-light-driven water oxidation system is reported that formed rapidly with an initial turnover frequency of approximately 8 x 10(-2) s(-1) and an estimated quantum yield of approximately 9%. Expand
The Ru-Hbpp water oxidation catalyst.
TLDR
Theoretical modeling at density functional and multireference second-order perturbation theory levels provides a microscopic mechanism for key steps in intermediate formation and oxygen evolution that are consistent with experimental kinetic data and also oxygen labeling experiments, monitored via mass spectrometry (MS), that unambiguously establish that oxygen-oxygen bond formation proceeds intramolecularly. Expand
Single-site, catalytic water oxidation on oxide surfaces.
TLDR
The surface-bound catalyst appears to retain the water oxidation mechanism found for [Ru(tpy)(bpm)(OH(2))](2+) and [Ru-Tpy)(bpz)( OH(2)](2%) in solution and acts as a surface electrocatalyst for sustained water oxidation. Expand
Mechanisms of water oxidation from the blue dimer to photosystem II.
TLDR
Application of density functional theory calculations to molecular and electronic structure supports the proposal of strong electronic coupling across the micro-oxo bridge and reveals similarities in the mechanism with the blue dimer and significant differences. Expand
Concerted O atom–proton transfer in the O—O bond forming step in water oxidation
TLDR
Microscopic details of O—O bond formation have been explored by quantum mechanical/molecular mechanical (QM/MM) simulations the results of which provide detailed insight into mechanism and a strategy for enhancing catalytic rates. Expand
Acid-base mechanism for ruthenium water oxidation catalysts.
TLDR
A mechanism is discovered that proceeds in analogous fashion to the monomer case, with all the most significant steps occurring at a single catalytic center within the dimer, which suggests a new set of strategies for the rational design of multicenter catalysts. Expand
...
1
2
...