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

Abstract

A family of Ru complexes based on the pentadentate ligand t5a 3– ((2,5-bis(6-carboxylatopyridin-2-yl)pyrrol-1-ide) and pyridine (py) that includes {Ru II(Ht5a-κ-N 2O)(py) 3} (1H II(κ-N 2O)), {Ru III(t5a-κ-N 3O 1.5)(py) 2} (2 III(κ-N 3O 1.5)), and {Ru IV(t5a-κ-N 3O 2)(py) 2}+ ({2 IV(κ-N3O 2)}+) has been prepared and thoroughly characterized. Complexes 1HII(κ-N 2O), 2 III(κ-N 3O 1.5), and {2 IV(κ-N 3O 2)}+ 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 2 III(κ-N 3O 1.5) have been studied by electrochemical methods (CV and DPV), showing its easy access to high oxidation states, thanks to the trianionic nature of the t5a 3– ligand. Under neutral to basic conditions complex {2 IV(κ-N3O 2)}+ undergoes aquation, generating {Ru IV(OH)(t5a-κ-N 2O)(py) 2} (2 IV(OH)(κ-N 2O)). Further oxidation of the complex forms {Ru V(O)(t5a-κ-N 2O)(py) 2} (2 V(O)(κ-N 2O)), which is a very efficient water oxidation catalyst, reaching a TOF MAX 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 2more » V(O)(κ-N 2O) 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.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [3];  [3];  [4];  [5];  [3]; ORCiD logo [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)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1425070
Report Number(s):
BNL-203210-2018-JAAM
Journal ID: ISSN 2155-5435
Grant/Contract Number:
SC0012704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Matheu, Roc, Ertem, Mehmed Z., Pipelier, Muriel, Lebreton, Jacques, Dubreuil, Didier, Benet-Buchholz, Jordi, Sala, Xavier, Tessier, Arnaud, and Llobet, Antoni. The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation. United States: N. p., 2018. Web. doi:10.1021/acscatal.7b03638.
Matheu, Roc, Ertem, Mehmed Z., Pipelier, Muriel, Lebreton, Jacques, Dubreuil, Didier, Benet-Buchholz, Jordi, Sala, Xavier, Tessier, Arnaud, & Llobet, Antoni. The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation. United States. doi:10.1021/acscatal.7b03638.
Matheu, Roc, Ertem, Mehmed Z., Pipelier, Muriel, Lebreton, Jacques, Dubreuil, Didier, Benet-Buchholz, Jordi, Sala, Xavier, Tessier, Arnaud, and Llobet, Antoni. Fri . "The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation". United States. doi:10.1021/acscatal.7b03638.
@article{osti_1425070,
title = {The Role of Seven-Coordination in Ru-Catalyzed Water Oxidation},
author = {Matheu, Roc and Ertem, Mehmed Z. and Pipelier, Muriel and Lebreton, Jacques and Dubreuil, Didier and Benet-Buchholz, Jordi and Sala, Xavier and Tessier, Arnaud and Llobet, Antoni},
abstractNote = {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.},
doi = {10.1021/acscatal.7b03638},
journal = {ACS Catalysis},
number = 3,
volume = 8,
place = {United States},
year = {Fri Jan 19 00:00:00 EST 2018},
month = {Fri Jan 19 00:00:00 EST 2018}
}

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