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Title: The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States

Journal Article · · Chemistry - A European Journal
 [1];  [1];  [1];  [2];  [3];  [1];  [4];  [2];  [1];  [5];  [6]
  1. Barcelona Inst. of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
  2. Free Univ. of Berlin (Germany). Inst. for Experimental Physics
  3. Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Dept.
  4. Yale Univ., New Haven, CT (United States). Dept. of Chemistry
  5. Autonomous Univ. of Barcelona (Spain). Dept. of Chemistry
  6. Barcelona Inst. of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Autonomous Univ. of Barcelona (Spain). Dept. of Chemistry
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The Ru complex [RuII(bda-κ-N2O2)(N-NH2)2], 1, (bda2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO+, acetonitrile (MeCN) or H2O ligands at oxidation states II and III. Complex 1 reacts with excess NO+ to form a Ru complex where the aryl amine ligands N-NH2 in 1 are transformed into diazonium salts (N-N2+ = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [RuII(bda-κ-N2O)(NO)(N-N2)2]3+, 23+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [RuII(bda-κ-N2O)(MeCN)(N-NH2)2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[RuII(bda-κ-(NO)3)(H2O)(N-NH3)2](H2O)n}2+, 42+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[RuIII(bda-κ-(NO)3.5)(H2O)(N-NH3)2](H2O)n}3+, 53+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystal XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N2O is the main coordination mode for 23+ and 3, an equilibrium that involves isomers with κ-N2O and κ-NO2 coordination modes and neighboring hydrogen bonded water molecules is observed for 42+ and 53+.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Brookhaven National Laboratory (BNL), Upton, NY (United States); Yale Univ., New Haven, CT (United States); Barcelona Inst. of Science and Technology (BIST), Tarragona (Spain); Autonomous Univ. of Barcelona (Spain); Free Univ. of Berlin (Germany)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Economy and Competitiveness (MINECO) (Spain); European Regional Development Fund (ERDF); Agency for Management of University and Research Grants (AGAUR) (Catalonia); German Research Foundation (DFG); German Federal Ministry of Education and Research (BMBF)
Grant/Contract Number:
SC0012704; SC0001059; CTQ2016-80058-R; CTQ2015-64261-R; SEV 2013-0319; ENE2016-82025-REDT; CTQ2016-81923-REDC; 2017-SGR-1631; Ha3265/6-1; 05K14KE1
OSTI ID:
1460704
Report Number(s):
BNL-207843-2018-JAAM; BNL-207859-2018-JAAM
Journal Information:
Chemistry - A European Journal, Vol. 24, Issue 49; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

References (42)

Structural Modifications of Mononuclear Ruthenium Complexes:  A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium-Catalyzed Water Oxidation journal December 2010
Highly Efficient Bioinspired Molecular Ru Water Oxidation Catalysts with Negatively Charged Backbone Ligands journal June 2015
Supramolecular Water Oxidation with Ru-bda-Based Catalysts journal November 2014
Evolution of O 2 in a Seven-Coordinate Ru IV Dimer Complex with a [HOHOH] − Bridge: A Computational Study journal March 2010
Highly Efficient Oxidation of Water by a Molecular Catalyst Immobilized on Carbon Nanotubes journal October 2011
Rearranging from 6- to 7-coordination initiates the catalytic activity: An EPR study on a Ru-bda water oxidation catalyst journal September 2017
Attachment of organic layers to conductive or semiconductive surfaces by reduction of diazonium salts journal January 2005
A Million Turnover Molecular Anode for Catalytic Water Oxidation journal November 2016
Molecular Water Oxidation Mechanisms Followed by Transition Metals: State of the Art journal December 2013
Understanding the eighteen-electron rule journal October 2006
Evaluation of Chromophore and Assembly Design in Light-Driven Water Splitting with a Molecular Water Oxidation Catalyst journal June 2016
Effect of metal-ligand bond distances on rates of electron-transfer reactions. Crystal structures of hexaammineruthenium(II) iodide, [Ru(NH3)6]I2, and hexaammineruthenium(III) tetrafluoroborate, [Ru(NH3)6][BF4]3 journal October 1971
A Self-Improved Water-Oxidation Catalyst: Is One Site Really Enough? journal November 2013
Mechanism of water oxidation by [Ru(bda)(L) 2 ]: the return of the “blue dimer” journal January 2015
Synthesis, structure and redox properties of a new ruthenium(II) complex containing the flexible tridentate ligand N,N-bis(2-pyridylmethyl)ethylamine, cis-fac-Ru(bpea)22+, and its homologue attached covalently to a polypyrrole film † journal January 2000
Insights into Ru-Based Molecular Water Oxidation Catalysts: Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities journal June 2013
A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II journal May 2016
Dinuclear Ru-Aqua Complexes for Selective Epoxidation Catalysis Based on Supramolecular Substrate Orientation Effects journal March 2014
Catalytic oxidation of water by an oxo-bridged ruthenium dimer journal July 1982
Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex journal August 2015
Structural Modifications of Mononuclear Ruthenium Complexes:  A Combined Experimental and Theoretical Study on the Kinetics of Ruthenium-Catalyzed Water Oxidation journal December 2010
Electronic Structure and Slow Magnetic Relaxation of Low-Coordinate Cyclic Alkyl(amino) Carbene Stabilized Iron(I) Complexes journal August 2014
How to make an efficient and robust molecular catalyst for water oxidation journal January 2017
A Million Turnover Molecular Anode for Catalytic Water Oxidation journal November 2016
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals journal July 2007
Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation journal August 2014
Hard and Soft Acids and Bases journal November 1963
Isolated Seven-Coordinate Ru(IV) Dimer Complex with [HOHOH] − Bridging Ligand as an Intermediate for Catalytic Water Oxidation journal August 2009
Visible Light Driven Water Splitting in a Molecular Device with Unprecedentedly High Photocurrent Density journal March 2013
Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO 2 -Protected Si Photoanodes journal August 2017
The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation journal January 2018
Highly Efficient Oxidation of Water by a Molecular Catalyst Immobilized on Carbon Nanotubes journal October 2011
A molecular ruthenium catalyst with water-oxidation activity comparable to that of photosystem II journal March 2012
Evolution of O 2 in a Seven-Coordinate Ru IV Dimer Complex with a [HOHOH] − Bridge: A Computational Study journal March 2010
New Dinuclear Ruthenium Complexes: Structure and Oxidative Catalysis journal March 2013
Eight steps preceding O–O bond formation in oxygenic photosynthesis—A basic reaction cycle of the Photosystem II manganese complex journal June 2007
Highly efficient and robust molecular water oxidation catalysts based on ruthenium complexes journal January 2014
Highly efficient and robust molecular ruthenium catalysts for water oxidation journal July 2012
Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell journal April 2015
Behavior of the Ru-bda Water Oxidation Catalyst Covalently Anchored on Glassy Carbon Electrodes journal May 2015
A Self-Improved Water-Oxidation Catalyst: Is One Site Really Enough? journal November 2013
Attachment of Organic Layers to Conductive or Semiconductive Surfaces by Reduction of Diazonium Salts journal August 2005

Cited By (7)

Quantum Chemical Study of the Mechanism of Water Oxidation Catalyzed by a Heterotrinuclear Ru 2 Mn Complex journal February 2019
Catalytic Oxidation of Water to Dioxygen by Mononuclear Ru Complexes Bearing a 2,6‐Pyridinedicarboxylato Ligand journal November 2018
Across the Board: Licheng Sun on the Mechanism of O−O Bond Formation in Photosystem II journal June 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 development of molecular water oxidation catalysts journal April 2019
Artificial photosynthesis: opportunities and challenges of molecular catalysts journal January 2019
Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis journal February 2020

Linked Research (2)

Figures / Tables (11)

Table 1(p. 13)table Table 1
Chart 1(p. 14)figure Chart 1
Scheme 1(p. 15)figure Scheme 1
Scheme 2(p. 16)figure Scheme 2
Scheme 3(p. 17)figure Scheme 3
Figure 1(p. 18)figure Figure 1
Figure 2(p. 19)figure Figure 2
Figure 3(p. 20)figure Figure 3
Figure 4(p. 20)figure Figure 4
Figure 5(p. 21)figure Figure 5
Figure 6(p. 21)figure Figure 6

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
water oxidation catalysis
water splitting
Ru complexes
water coordination
frustrated coordination site
Ru-bda complexes