Abstract
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 the final products.
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