A computational study of oxidation of ruthenium porphyrins via ORu(IV) and ORu(VI)O species.
An unrestricted density functional theory (UDFT) was applied to study the oxidation of ruthenium porphyrins, [RuP], via an interaction with molecular oxygen. The important role of dimeric [RuP] complexes, i.e. [RuP]-O2-[RuP], in the oxidation mechanism and particular in the cleavage of O-O bond of molecular oxygen has been studied. Geometries and relative Gibbs free energies of the intermediate Ru-complexes, i.e. dimeric oxo-Ru-porphyrins and O2Ru(II)-(or O2- Ru(III))-, ORu(IV)- and ORu(VI)O-porphyrins, were evaluated along the proposed reaction pathway. The detailed thermodynamic data of the oxidation reaction [Ru(II)P] --> O[Ru(IV)P] --> O[Ru(VI)P]O and important aspects of the vibrational spectra of an oxo-[RuP] has been presented.
Zierkiewicz
Wiktor
W
Organic Chemistry, School of Chemistry and Engineering, Royal Institute of Technology (KTH), S-10044, Stockholm, Sweden.
Privalov
Timofei
T
D003198:Computer Simulation; D008024:Ligands; D008665:Metalloporphyrins / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012428:Ruthenium / Q000737:chemistry*; D013816:Thermodynamics
D008024:Ligands; D008665:Metalloporphyrins; D012428:Ruthenium; D010100:Oxygen