Kinetics and mechanism of the Co(II)-assisted oxidation of thioureas by dioxygen.
Catalytic oxidation of N,N'-dimethylthiourea and thiourea by dioxygen in water using a new cobalt(II) complex of octasulfophenyltetrapyrazinoporphyrazine was performed under mild conditions. The reaction is shown to include the formation of an intermediate anionic five-coordinate complex followed by an unusual two-electron oxidation to produce the corresponding urea and elemental sulfur (S8). Kinetic and thermodynamic parameters for the different reaction steps of the process were determined. Drastic differences in catalytic activity of cobalt and iron octasulfophenyltetrapyrazinoporphyrazines were observed.
Kudrik
Evgeny V
EV
Institute for Inorganic Chemistry, University of Erlangen-Nurnberg, Egerlandstrasse 1, 91058 Erlangen, Germany.
Theodoridis
Alexander
A
van Eldik
Rudi
R
Makarov
Sergei V
SV
D002384:Catalysis; D003035:Cobalt / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007700:Kinetics; D008024:Ligands; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013890:Thiourea / Q000031:analogs & derivatives / Q000737:chemistry*; D014867:Water / Q000737:chemistry
D008024:Ligands; D009942:Organometallic Compounds; D014867:Water; D003035:Cobalt; D013890:Thiourea; D010100:Oxygen