%0 Journal Article %T Platinum-oxygen Bond Formation: Kinetic and Mechanistic Studies %J Inorganic Chemistry Research %I Iranian Chemical Society %Z 2538-1865 %A Hadadi, Elahe %A Nabavizadeh, S. Masoud %A Niroomand Hosseini, Fatemeh %D 2019 %\ 12/01/2019 %V 3 %N 2 %P 117-128 %! Platinum-oxygen Bond Formation: Kinetic and Mechanistic Studies %K Oxidative addition %K platinum %K kinetic and mechanism %R 10.22036/icr.2019.210340.1057 %X Reaction of [PtMe(C^N)(SMe2)] (C^N = 2-phenylpyridinate (ppy); 1a, C^N = benzo[h]quinolate, (bhq); 1b) with hydrogen peroxide gives the platinum(IV) complexes trans-[PtMe(OH)2(C^N)(H2O)] (C^N = ppy; 3a, C^N = bhq, 3b) bearing platinum-oxygen bonds. The Pt(II) complexes 1a and 1b have 5dπ(Pt)→π*(C^N) MLCT band in the visible region which is used to easily follow the kinetic of its reaction with H2O2. The kinetics and mechanism of Pt−O bond formation have been experimentally and theoretically investigated, showing the simple second-order kinetics; rate = k2[H2O2][Pt(II) complex]. The Pt(IV) products were characterized by NMR spectroscopy and elemental analysis. The geometries and the nature of the frontier molecular orbitals of Pt(IV) complexes containing Pt-O bonds were also studied by means of the density functional theory. Complex 3b is unstable during the crystallization process in CH2Cl2/acetone and gives the binuclear complex [Pt2Me2(Cl)2(μ-OH)2(bhq)2], 4. %U https://www.inorgchemres.org/article_101647_5ec120f744b9487708330ab6103b866b.pdf