2026-04-17T23:31:57Zhttps://recercat.cat/oai/request
oai:recercat.cat:2072/3746052024-12-20T19:18:45Zcom_2072_300912com_2072_4427col_2072_301309
RECERCAT author Vereshchuk, Nataliia author Matheu, Roc author Benet-Buchholz, Jordi author Pipelier, Muriel author Lebreton, Jacques author Dubreuil, Didier author Tessier, Arnaud author Gimbert-Suriñach, Carolina author Ertem, Mehmed Z. author Llobet, Antoni 2020-04-14T12:08:30Z2024-04-23T10:18:58Z 2021-02-10T01:45:07Z2024-04-23T10:18:58Z 2020-02-11 http://hdl.handle.net/2072/374605 https://doi.org/10.1021/jacs.9b11935 A new Ru complex containing the deprotonated 2,2':6',2''-terpyridine,6,6''-diphosphonic acid (H4tPa) and pyridine (py) of general formula, [RuII(H3tPa--N3O)(py)2]+, 2+, has been prepared and thoroughly characterized by means of spectroscopic, electrochemical techniques, X-ray diffraction analysis and with 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 tPa4- ligand. However, at oxidation state IV complex 2+, it 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 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 [RuIII(tPaO-- N2OPOC)(py)2]2, 42, where tPaO5- is 3-hydroxo-[2,2':6',2''-terpyridine]-6,6''-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 42-, 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 42- turns out to be an exceptional water oxidation catalyst achieving record high TOFmax in the order of 16,000 s-1. A mechanistic analysis complemented with DFT calculations has also 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. eng L'accés als continguts d'aquest document queda condicionat a l'acceptació de les condicions d'ús establertes per la següent llicència Creative Commons:http://creativecommons.org/licenses/by-nc-nd/4.0/ Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion URL https://recercat.cat/bitstream/2072/374605/5/213_%20Nataliia_JACS_2020.pdf File MD5 baf23bf7ebad073beafec8a96d0a588b 1553209 application/pdf 213_ Nataliia_JACS_2020.pdf URL https://recercat.cat/bitstream/2072/374605/1/213_%20Nataliia_JACS_2020.pdf.txt File MD5 2d6202830fbd08f910590b5018d2bb6b 43479 text/plain 213_ Nataliia_JACS_2020.pdf.txt