Understanding the two-electron redox chemistry of water oxidation catalyst Cis,cis-[(bpy)2RuIII,IV,VOHx]2Oy+

INOR 836

Xiaofan Yang, xy1@indiana.edu and Mu-Hyun Baik, mbaik@indiana.edu. Department of Chemistry, Indiana University, 800 East Kirkwood Ave., Bloomington, IN 47405-7102
The apparently simultaneous removal of two electrons from a redox active molecule is unusual, because the removal of a second electron should be more difficult than the first due to a stronger Coulombic forces in the one-electron oxidized molecule. There is convincing experimental evidence that the diruthenium complex cis,cis-[(bpy)2RuIII(OH2)]2O4+ (bpy: 2,2'-bipyridine), which is capable of catalyzing water oxidation at ambient conditions, displays a two-electron redox behavior during the overall 4-electron-4-proton redox process that leads to the catalytically active cis,cis-[(bpy)2RuVO]2O4+ complex. Unfortunately, there is currently no agreement regarding the redox species involved. We used density functional methods to simulate the redox behavior and delineate some of the conflicting experimental results.
 

Inorganic Catalysts
8:30 AM-12:10 PM, Wednesday, August 22, 2007 BCEC -- 209, Oral

Division of Inorganic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007