A Ru(II) Bis-terpyridine-like Complex that Catalyzes Water Oxidation: The Influence of Steric Strain

The complexation of 2,9-dicarboxy-1,10-phenanthroline (DPA) with [Ru­(tpy)­Cl₃] (tpy = 2,2′;6,2″-terpyridine) provides a six-coordinate species in which one carboxyl group of DPA is not bound to the Ru­(II) center. A more soluble tri-<i>t-</i>butyl tpy analogue is also prepared. Upon oxidation, neither species shows evidence for intramolecular trapping of a seven-coordinate intermediate. The role of the tpy ligand is revealed by the preparation of [Ru­(tpy)­(phenq)]²⁺ (phenq = 2-(quinol-8′-yl)-1,10-phenanthroline) that behaves as an active water oxidation catalyst (TON = 334). This activity is explained by the expanded coordination geometry of the phenq ligand that can form a six-membered chelate ring that better accommodates the linear arrangement of axial ligands required for optimal pentagonal bipyramid geometry. When a 1,8-naphthyidine ring is substituted for each of the two peripheral pyridine rings on tpy, increased crowding in the vicinity of the metal center impedes acquisition of the prerequisite reaction geometry