Single Site Isomeric Ru WOCs with an Electron-Withdrawing Group: Synthesis, Electrochemical Characterization, and Reactivity

The synthetic intermediate cis(out),cis-[Ru(Cl)(2)(HL)(DMSO)(2)], 1 (DMSO = dimethyl sulfoxide), and four new mononuclear ruthenium complexes with general formula out/in-[Ru(HL)(trpy)(X)](m+) (trpy = 4-tert-butylpyridine; X = Cl-, m = 1, 2a(+) and 2b(+); X = H2O, m = 2, 3a(2+) and 3b(2+)) based on the ligand 1H-pyrazole-3-carboxylic acid, 5-(2-pyridinil)-, ethyl ester (HL), are synthesized and characterized by analytical, spectroscopic, and electrochemical methods. A linkage isomerism is observed for a DMSO moiety of 1, and relevant thermodynamics and kinetics values are obtained through electrochemical experiments and compared to literature. Different synthetic routes are developed to obtain isomeric 2a(+) and 2b(+), with different relative yields. Water oxidation activity of 3a(2+) and 3b(2+) is analyzed by means of electrochemical methods, through foot of the wave analysis, yielding k(obs) values of 1.00 and 2.23 s(-1), respectively. Chemically driven water oxidation activity is tested using [(NH4)(2)Ce(NO3)(6)] as sacrificial electron acceptor, and turnover number (TON) and turnover frequency (TOF) values of TON = 10.8 and TOFi = 58.2 x 10(-3) s(-1) for 3a(2+) and TON = 4.2 and TOFi = 15.4 x 10(-3) s(-1) for 3b(2+) are obtained.