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Stable trans isomer as the kinetic and theromodynamic product for the oxidative addition of MeI to cycloplatinated(II) complexes comprising isocyanide ligands
Author(s) -
Shahsavari Hamid R.,
Aghakhanpour Reza Babadi,
HosseinAbadi Mojdeh,
Kia Reza,
Raithby Paul R.
Publication year - 2018
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.4216
Subject(s) - chemistry , oxidative addition , isocyanide , nuclear magnetic resonance spectroscopy , medicinal chemistry , reductive elimination , stereochemistry , catalysis , organic chemistry
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‐ t Bu > 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).