Synthesis and characterization of New Mononuclear Ru (II) Polypyridine Complexes with Catalytic Activity

PEYROT, ANALIA MERCEDES; ZELAYA, MARÍA PRISCILA; ALBORÉS, PABLO; FAGALDE, FLORENCIA

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

WILEY-V C H VERLAG GMBH

Año: 2023

1434-1948

In this work we report the synthesis and physicochemical characterization ofnew chloroand aquamononuclear Ru (II) complexesof formula [Ru(LLL)(dpp)Cl]PF6 and [Ru(LLL)(dpp)OH2](PF6)2(withLLL= tpy =2,2’:6’,2’’-terpyridine; tptz=2,4,6-tris(2-pyridyl)-1,3,5-triazineand dpp=2,3-bis(2-pyridil)pyrazine).For complex [Ru(tptz)(dpp)Cl]PF6was determined the complete structure by X-ray diffraction. Catalytic studies ofaqua-complexesrevealed that they are active against the water oxidation reaction at pH=1 using cerium ammonium nitrate (CAN) as sacrificial oxidant. Also,we were able to establish reaction mechanism and rate constants of each stage of the catalytic cycle, turnover frequency (TOF) and turnover number (TON). The experimental TON value forthe aqua complexes was very close to theoretical value of 7.5, indicating a high degree of recovery.DFT and TD-DFT calculations of complexeswere consistent with experimental results and allowed the complete assignment of its UV–Visible bands, and redox states