From Ru-bda to Ru-bds: a step forward to highly efficient molecular water oxidation electrocatalysts under acidic and...

Significant advances during the past decades in the design and studies of Ru complexes with polypyridine ligands have led to the great development of molecular water oxidation catalysts and understanding on the O-O bond formation mechanisms. Here we report a Ru-based molecular water oxidation catalyst [Ru(bds)(pic)₂] (Ru-bds; bds^2- = 2,2'-bipyridine-6,6'-disulfonate) containing a tetradentate, dianionic sulfonate ligand at the equatorial position and two 4-picoline ligands at the axial positions. This Ru-bds catalyst electrochemically catalyzes water oxidation with turnover frequencies (TOF) of 160 and 12,900 s^-1 under acidic and neutral conditions respectively, showing much better performance than the state-of-art Ru-bda catalyst. Density functional theory calculations reveal that (i) under acidic conditions, the high valent Ru intermediate Ru^V=O featuring the 7-coordination configuration is involved in the O-O bond formation step; (ii) under neutral conditions, the seven-coordinate Ru^IV=O triggers the O-O bond formation; (iii) in both cases, the I2M (interaction of two M-O units) pathway is dominant over the WNA (water nucleophilic attack) pathway.