2026-04-14T03:27:13Zhttps://recercat.cat/oai/request

oai:recercat.cat:2072/3058472026-01-15T14:12:37Zcom_2072_300912com_2072_4427col_2072_301309

00925njm 22002777a 4500 dc Roeser, Stephan author Bozoglian, Fernando author Richmond, Craig J. author League, Aaron. B. author Ertem, Mehmed. Z author Francas, Laia author Miro, Pere author Benet-Buchholz, Jordi author Cramer, Christopher J. author Llobet, Antoni author 2016 <p> A series of symmetric and non-symmetric dinuclear Ru complexes of general formula {[Ru(R2-trpy)(H2O)][Ru(R3-trpy)(H2O)](&mu;-R1-bpp)}3+ where trpy is 2,2&prime;:6&prime;,2&prime;&prime;-terpyridine, bpp&minus; is 3,5-bis(2-pyridyl)-pyrazolate and R1, R2 and R3 are electron donating (ED) and electron withdrawing (EW) groups such as Me, MeO, NH2 and NO2 have been prepared using microwave assisted techniques. These complexes have been thoroughly characterized by means of analytical (elemental analysis), spectroscopic (UV-vis, NMR) and electrochemical (CV, SQWV, CPE) techniques. The single crystal X-ray structures for one acetate- and one chloro-bridged precursor have also been solved. Kinetic analysis monitored by UV-vis spectroscopy reveals the electronic effects exerted by the ED and EW groups on the substitution kinetics and stoichiometric water oxidation reaction. The catalytic water oxidation activity is evaluated by means of chemically (CeIV), electrochemically, and photochemically induced processes. It is found that, in general, ED groups do not strongly affect the catalytic rates whereas EW groups drastically reduce catalytic rates. Finally, DFT calculations provide a general and experimentally consistent view of the different water oxidation pathways that can operate in the water oxidation reactions catalyzed by these complexes.</p> http://hdl.handle.net/2072/305847 https://doi.org/10.1039/C6CY00197A Water Oxidation Catalysis with Ligand Substituted Ru-bpp-type Complexes