404577-10-2Relevant academic research and scientific papers
Kinetics and mechanism of cleavage of the oxygen-oxygen bond in hydrogen peroxide and dibenzoyl peroxide by arylplatinum(II) complexes
Rashidi,Nabavizadeh,Hakimelahi,Jamali
, p. 3430 - 3434 (2007/10/03)
Reaction of [PtAr2(NN)] (Ar = Ph, p-MeC6H4,m-MeC6H4 or p-MeOC6H4; NN = 2,2′-bipyridyl or 1,10- phenanthroline) with R2O2, in which R = H or C(=O)Ph, gives the platinum(IV) complexes cis,trans- [PtAr2(OH)2(NN)] or [PtAr2(OCOPh)2(NN)] (as a 5:1 mixture of cis,trans and cis,cis isomers), respectively. The kinetics of these oxidative addition reactions in acetone was followed by visible spectrophotometry between 10 and 40°C. The reactions followed simple second-order kinetics, rate = k2[PtAr2(NN)][peroxide], and the rates were insensitive to change of solvent. Activation parameters have been determined and large negative values for ΔS≠ were obtained. A mechanism is suggested which involves a concerted three-center transition state, followed by homolytic cleavage of the O-O bond and formation of thefinal products.
