Ligand (biochemistry)

Receptor

Organic chemistry

Stereochemistry

Crystallography

Crystal structure

Deprotonation

Coordination sphere

Density functional theory

Catalysis

Computational chemistry

Medicinal chemistry

Chemistry

Oxidation state

Pyridine

Phosphonate

Metal

Coordination complex

Intramolecular force

Terpyridine

Biochemistry

Ruthenium

Journal of the American Chemical Society

A new Ru complex containing the deprotonated 2,2′:6′,2′′-terpyridine-6,6′′-diphosphonic acid (H4tPa) and pyridine (py) of general formula [RuII(H3tPa-κ-N3O)(py)2]+, 2+, has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2+ presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa4– ligand. However, at oxidation state IV, complex 2+ becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH– group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [RuIII(tPaO-κ-N2OPOC)(py)2]2–, 42–, where tPaO5– is the 3-(hydroxo-[2,2′:6′,2′′-terpyridine]-6,6′′-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 42–, has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 42– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOFmax) on the order of 16 000 s–1. A mechanistic analysis complemented with DFT calculations has also been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis