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

The Ru complex [Ru II(bda-κ-N 2O 2)(N-NH 2) 2], 1, (bda 2- = (2,2'-bipyridine)-6,6'-dicarboxylate; N-NH 2 = 4-(pyridin-4-yl)aniline) is used as a synthetic intermediate to prepare Ru-bda complexes that contain the NO +, acetonitrile (MeCN) or H 2O ligands at oxidation states II and III. Complex 1 reacts with excess NO + to form a Ru complex where the aryl amine ligands N-NH 2 in 1 are transformed into diazonium salts (N-N 2 + = 4-(pyridin-4-yl)benzenediazonium)) together with the formation of a new Ru-NO group at the equatorial zone, to generate [Ru II(bda-κ-N 2O)(NO)(N-N 2) 2] 3+, 2 3+. Similarly, complex 1 can also react with a coordinating solvent, such as MeCN, at room temperature leading to complex [Ru II(bda-κ-N 2O)(MeCN)(N-NH 2) 2], 3. Finally in acidic aqueous solutions solvent water coordinates the Ru center forming {[Ru II(bda-κ-(NO) 3)(H 2O)(N-NH 3) 2](H 2O) n} 2+, 4 2+, that is strongly hydrogen bonded with additional water molecules at the second coordination sphere. We have additionally characterized the one electron oxidized complex {[Ru III(bda-κ-(NO) 3.5)(H 2O)(N-NH 3) 2](H 2O) n} 3+, 5 3+. The coordination mode of the complexes has been studied both in the solid state and in solution through single-crystalmore » XRD, X-ray absorption spectroscopy, variable-temperature NMR and DFT calculations. While the κ-N 2O is the main coordination mode for 2 3+ and 3, an equilibrium that involves isomers with κ-N 2O and κ-NO 2 coordination modes and neighboring hydrogen bonded water molecules is observed for 4 2+ and 5 3+.« less
Authors:
 [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
Publication Date:
Report Number(s):
BNL-207843-2018-JAAM; BNL-207859-2018-JAAM
Journal ID: ISSN 0947-6539
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
Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 24; Journal Issue: 49; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Research Org:
Brookhaven National Lab. (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 Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 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)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; water oxidation catalysis; water splitting; Ru complexes; water coordination; frustrated coordination site; Ru-bda complexes
OSTI Identifier:
1460704

Matheu, Roc, Ghaderian, Abolfazl, Francas, Laia, Chernev, Petko, Ertem, Mehmed, Benet-Buchholz, Jordi, Batista, Victor, Haumann, Michael, Gimbert-Surinach, Carolina, Sala, Xavier, and Llobet, Antoni. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States. United States: N. p., Web. doi:10.1002/chem.201801236.
Matheu, Roc, Ghaderian, Abolfazl, Francas, Laia, Chernev, Petko, Ertem, Mehmed, Benet-Buchholz, Jordi, Batista, Victor, Haumann, Michael, Gimbert-Surinach, Carolina, Sala, Xavier, & Llobet, Antoni. The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States. United States. doi:10.1002/chem.201801236.
Matheu, Roc, Ghaderian, Abolfazl, Francas, Laia, Chernev, Petko, Ertem, Mehmed, Benet-Buchholz, Jordi, Batista, Victor, Haumann, Michael, Gimbert-Surinach, Carolina, Sala, Xavier, and Llobet, Antoni. 2018. "The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States". United States. doi:10.1002/chem.201801236.
@article{osti_1460704,
title = {The Behavior of the Ru-bda Water Oxidation Catalysts at Low Oxidation States},
author = {Matheu, Roc and Ghaderian, Abolfazl and Francas, Laia and Chernev, Petko and Ertem, Mehmed and Benet-Buchholz, Jordi and Batista, Victor and Haumann, Michael and Gimbert-Surinach, Carolina and Sala, Xavier and Llobet, Antoni},
abstractNote = {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+.},
doi = {10.1002/chem.201801236},
journal = {Chemistry - A European Journal},
number = 49,
volume = 24,
place = {United States},
year = {2018},
month = {6}
}