Abstract
DFT investigation of MeI oxidative addition reaction of the phosphine chelating platinum(II) complexes, [PtMe2(Me2P(CH2)nPMe2)] (n = 1–4) to afford the organoplatinum(IV) complexes, [PtMe3I(Me2P(CH2)nPMe2)], is reported. The first step of the oxidative addition reaction that proceeds via the usual SN2 mechanism is the nucleophilic attack of Pt center of platinum(II) complex to carbon atom of MeI. The reaction proceeds by formation of a transition state, which includes the Pt…C…I fragment, followed by formation of the intermediate [PtMe3(Me2P(CH2)nPMe2)]+I− with the incoming Me group in the apical position of five-coordinate intermediate and with the iodide ion out of coordination sphere of Pt(IV) intermediate. The effect of the P–Pt–P bite angle of phosphine chelate on the energy barrier of the reaction has been investigated in terms of the length of the diphosphine ligand backbone. The DFT studies are in agreement with the experimental findings.
Published Version
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