Insights into Ru-Based Molecular Water Oxidation Catalysts : Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities

• A series of Ru-bda water oxidation catalysts [Ru(bda)L-2] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; L = [HNEt3][3-SO3-pyridine], 1; 4-(EtOOC)-pyridine, 2; 4-bromopyridine, 3; pyridine, 4; 4-methoxypyridine, 5; 4-(Me2N)-pyridine, 6; 4-[Ph(CH2)(3)]-pyridine, 7) were synthesized with election-donating/-withdrawing groups and hydro-philic/hydrophobic groups in the axial ligands. These complexes were characterized by H-1 NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and electrochemistry. In addition, complexes 1 and 6 were further identified by single crystal X-ray crystallography, revealing a highly distorted octahedral configuration of the Ru coordination sphere. All of these complexes are highly active toward Ce-IV-driven (Ce-IV = Ce(NH4)(2)(NO3)(6)) water oxidation with oxygen evolution rates up to 119 mols of O-2 per mole of catalyst per second. Their structure-activity relationship was investigated. Electron-withdrawing and noncovalent interactions (attraction) exhibit positive effect on the catalytic activity of Ru-bda catalysts.

Subject headings

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Keyword

Mononuclear Ruthenium Complexes; O-O Bond; Iridium Complexes; Redox Properties; Functional-Model; Photosystem-Ii; O-2 Evolution; Efficient; Ligands; Site

Publication and Content Type

ref (subject category)

art (subject category)