Facile activation of the C−I bond of primary alkyl halides by Pt(II) complexes having a benzothiazole ligand

Publication date: Available online 19 February 2020Source: Inorganica Chimica ActaAuthor(s): S. Masoud Nabavizadeh, Fatemeh Raoof, Fatemeh Pakpour, Laleh Shafiei Sarvestani, Fatemeh Niknam, Fatemeh Niroomand Hosseini, S. Jafar HoseiniAbstractThe alkyl halides, RI (MeI and EtI), were oxidatively added to a Pt(II) complex [PtMe2(pbt)], 1, in which pbt = 2-(2-pyridyl)benzothiazole, to give the Pt(IV) complexes [PtIRMe2(pbt)] (R = Me; 2 and R = Et; 3). Kinetics of the reactions in toluene and acetone were studied using UV-vis spectroscopy between 5 and 40 °C and an SN2 mechanism was suggested. The reaction of MeI with complex 1 was considerably faster than EtI. The reactions followed second-order kinetics, rate = k2[1][RI], and the rates in the polar solvent acetone were faster than those in the nonpolar solvent toluene. Activation parameters have been determined and large negative values for ΔS‡ were obtained. The results were also confirmed using DFT calculations. The computational investigations were used to determine the geometry of the species involved in the suggested mechanism and energy barriers.Graphical abstractKinetic and mechanism of addition of alkyl halides (RI= MeI and EtI) to [PtMe2(pbt)], in which pbt = 2-(2-pyridyl)benzothiazole, to give the Pt(IV) complexes [PtIRMe2(pbt)] were investigated.
Source: Inorganica Chimica Acta - Category: Chemistry Source Type: research
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