Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

Vereshchuk, Nataliia; Matheu, Roc; Benet-Buchholz, Jordi; Pipelier, Muriel; Lebreton, Jacques; Dubreuil, Didier; Tessier, Arnaud; Gimbert-Suriñach, Carolina; Ertem, Mehmed Z.; Llobet, Antoni

doi:10.1021/jacs.9b11935

Title: Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

Journal Article · Tue Feb 11 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11935· OSTI ID:1608772

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Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Rovira i Virgili University (URV), Tarragona (Spain). Dept. of Physical and Inorganic Chemistry
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
Univ. of Nantes (France)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Barcelona Institute of Science and Technology (BIST), Tarragona (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. Autonoma de Barcelona (Spain)

A new Ru complex containing the deprotonated 2,2':6',2"-terpyridine-6,6"-diphosphonic acid (H₄tPa) and pyridine (py) of general formula [Ru^II(H₃tPa-κ-N³O)(py)₂]⁺, 2⁺, has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2⁺ presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa^4– ligand. Yet, at oxidation state IV, complex 2⁺ becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH^– group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [Ru^III(tPaO-κ-N²O_PO_C)(py)₂]^2–, 4^2–, where tPaO^5– is the 3-(hydroxo-[2,2':6',2"-terpyridine]-6,6"-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 4^2–, has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 4^2– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOF_max) on the order of 16 000 s^–1. A mechanistic analysis complemented with DFT calculations has further been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704; CTQ2016- 80058-R; CTQ2015-73028-EXP; SEV 2013-0319; ENE2016-82025-REDT; CTQ2016-81923-REDC

OSTI ID:: 1608772

Report Number(s):: BNL-213794-2020-JAAM

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 11; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 56 works

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