Abstract
We present a previously unknown series of cyclometalated platinum(IV) NHC complexes, obtained by oxidative addition of iodine, iodomethane, and different benzyl bromides to platinum(II) complexes with cyclometalated C^C* dibenzofuran, dibenzothiophene, and phenylimidazole ligands together with an acetylacetonate ligand. All compounds were characterized by standard techniques (1H, 13C, and 195Pt NMR and elemental analysis), and for three complexes, solid-state structures could be obtained. DFT calculations (B3LYP(d3)/def2-TZVPP including dispersion interactions in dichloromethane and acetone) were performed to investigate the mechanism of the oxidation and explain the exclusive formation of the observed trans products.
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