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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; bds2- = 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 RuV=O featuring the 7-coordination configuration is involved in the O-O bond formation step; (ii) under neutral conditions, the seven-coordinate RuIV=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.
Pubmed ID: 33446649
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Ab initio molecular modeling software program that computes an array of molecular properties such as multipole moments, polarizabilities, and electrostatic potential. It can also map reaction coordinates between reactants, products, and transition states.
View all literature mentionsInstitution which compiles and distributes small molecule crystallography data from the Cambridge Structural Database (CSD), a repository of experimentally determined organic and metal-organic crystal structures. CCDC also produces associated knowledge-based application software for structural chemists. Structures deposited with CCDC are made publically available for download at the point of publication or at consent from the depositor.
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