Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands

Hamid R. Shahsavari, Reza Babadi Aghakhanpour, Mojdeh Hossein-Abadi, Reza Kia, Paul R. Raithby

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Abstract

The present investigation introduces a new series of cycloplatinated(II) complexes, with the general formula Pt(O-bpy)(Me)(CN-R)] (R = benzyl, 2-naphtyl and tert-butyl), which are able to generate the stable trans-Pt(IV) product in the solution after the reaction with iodomethane. In fact, the trans product is both the kinetic and thermodynamic product of the reaction; this observation was supported by DFT calculations. These Pt(II) complexes are supported by 2,2'-bipyridine N-oxide (O-bpy) and one of several isocyanides as the cyclometalated and ancillary ligands, respectively. These new Pt(II) complexes undergo oxidative addition with MeI to give the corresponding trans-Pt(IV) complexes. All the complexes were identified employing the multi-nuclear NMR spectroscopy and single crystal X-ray crystallography. The kinetic investigations were also performed for the oxidative addition reactions in order to measure the reaction rates; the reaction was followed by UV-Vis spectroscopy. The rates obtained follow the trend CN-tBu > CN-Bz > CN-2 Np for the CN-R ligands in the Pt(II) complexes. The order can be related to the degree of electron-donation of the R group (tert-butyl > benzyl > 2-naphtyl).

Original languageEnglish
Article numbere4216
Number of pages11
JournalApplied Organometallic Chemistry
Volume32
Issue number4
Early online date5 Jan 2018
DOIs
Publication statusPublished - 1 Apr 2018

Keywords

  • Cycloplatinated complexes
  • DFT calculations
  • Isocyanide ligands
  • Kinetic
  • Mechanism
  • Oxidative addition

ASJC Scopus subject areas

  • Chemistry(all)
  • Inorganic Chemistry

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