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The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation

Journal Article · · ACS Catalysis
 [1];  [2];  [3];  [3];  [3];  [4];  [5];  [3];  [6]
  1. The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. Rovira i Virgli, Tarragona (Spain)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Univ. de Nantes (France)
  4. The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
  5. Univ. Autonoma de Barcelona (Spain)
  6. The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. Autonoma de Barcelona (Spain)
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A family of Ru complexes based on the pentadentate ligand t5a3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {RuII(Ht5a-κ-N2O)(py)3} (1HII(κ-N2O)), {RuIII(t5a-κ-N3O1.5)(py)2} (2III(κ-N3O1.5)), and {RuIV(t5a-κ-N3O2)(py)2}+ ({2IV(κ-N3O2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N2O), 2III(κ-N3O1.5), and {2IV(κ-N3O2)}+ have been investigated in solution by spectroscopic methods (NMR, UV–vis) and in the solid state by single-crystal X-ray diffraction analysis and complemented by density functional theory (DFT) calculations. The redox properties of complex 2III(κ-N3O1.5) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a3– ligand. Under neutral to basic conditions complex {2IV(κ-N3O2)}+ undergoes aquation, generating {RuIV(OH)(t5a-κ-N2O)(py)2} (2IV(OH)(κ-N2O)). Further oxidation of the complex forms {RuV(O)(t5a-κ-N2O)(py)2} (2V(O)(κ-N2O)), which is a very efficient water oxidation catalyst, reaching a TOFMAX value of 9400 s–1 at pH 7.0, as measured via foot of the wave analysis. The key to fast kinetics for the catalytic oxidation of water to dioxygen by 2V(O)(κ-N2O) is due not only to the easy access to high oxidation states but also to the intramolecular hydrogen bonding provided by the noncoordinated dangling carboxylate at the transition state, as corroborated by DFT calculations.
Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0012704
OSTI ID:
1425070
Report Number(s):
BNL-203210-2018-JAAM
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 3 Vol. 8; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

Behavior of Ru-bda Water-Oxidation Catalysts in Low Oxidation States journal August 2018
Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru 2 Mn Complex journal February 2019
Axial Ligand Effects of Ru-BDA Complexes in the O-O Bond Formation via the I2M Bimolecular Mechanism in Water Oxidation Catalysis: Axial Ligand Effects of Ru-BDA Complexes in the O-O Bond Formation via the I2M Bimolecular Mechanism in Water Oxidation Catalysis journal February 2019
The Art of Splitting Water: Storing Energy in a Readily Available and Convenient Form: The Art of Splitting Water: Storing Energy in a Readily Available and Convenient Form journal March 2019
Artificial photosynthesis: opportunities and challenges of molecular catalysts journal January 2019
Kinetics and mechanisms of catalytic water oxidation journal January 2019
Low overpotential water oxidation at neutral pH catalyzed by a copper( ii ) porphyrin journal January 2019
Reversible pyrrole-based proton storage/release in ruthenium( ii ) complexes journal January 2019
Pentanuclear iron catalysts for water oxidation: substituents provide two routes to control onset potentials journal January 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY