Kinetic Studies of Oxidative Addition Reaction of Arylplatinum(II) Complex Containing 4,4′‐Bipyridine and Calculation of Activation Parameters

Abstract

New complexes of arylplatinum(II) and arylplatinum(IV) containing a bridging ligand, 4,4′‐bipyridine, were synthesized by the reaction of starting material of platinum(II) including para‐tolyl groups,[(p‐MeC6H4)2Pt(SMe2)2], with the 4,4′‐bipyridine ligand in 1:1 molar stoichiometry. In the synthesized complexes, the ligand was bonded to the platinum center through the nitrogen donor atoms. To investigate the kinetic reaction of the platinum(II) complex with iodomethane (CH3‐I) as a reagent, the oxidative addition reaction of this reagent with Pt(II) was performed in dichloromethane and a Pt(IV) complex with the octahedral geometry was formed. The synthesized complexes have been characterized by different spectroscopic methods such as FT‐IR, 1H NMR, UV–vis, and elemental analysis. Moreover, the conductivity measurements showed nonelectrolyte characteristics for these complexes. The obtained data showed that the complexes have 1:1 metal‐to‐ligand molar ratio. Also, the oxidative addition reaction of CH3I with the arylplatinum(II) complex at different temperatures was used for obtaining kinetic parameters such as rate constants, activation energy, entropy, and enthalpy of activation using the Microsoft Excel solver. From the acquired data, an SN2 mechanism was suggested for the oxidative addition reaction.

Novel arylplatinum complexes with 2,2′‐dimethyl‐4,4′‐bithiazole: Synthesis, characterization, single crystal structure determination, and investigation of CT‐DNA interaction

“…Moreover, the coupling constants of platinum and ortho hydrogens were calculated as 3 J(PtH o ) = 75.80 Hz and 3 J(PtH o ) = 78.21 Hz for 1 and 2 complexes, respectively. [32][33][34][35][36]38]…”

“…Recently, the synthesis of some organoplatinum complexes with different ligands and geometries has been reported. [5,11,13,22,[32][33][34][35][36][37][38][39][40][41][42] In this contribution, we report the synthesis of novel heteroleptic platinum complexes containing di-aryl and dm4bt. Characterizations of these complexes are done by different methods like ultravioletvisible (UV-Vis), Fourier-transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance ( 1 H NMR), elemental analysis, and conductivity.…”