A novel coordination mode of kappa(1)-N-Br-pyridylbenz-(imida, oxa or othia)-zole to Pt(II): synthesis, characterization, electrochemical and structural analysis

Herein, three novel Pt(II) complexes with formula [trans-Pt(Br-PyBenz-X)(Cl)(2)(DMSO)] (1-3) having Br-pyridylbenz-(imida, oxa or othia)-zole (L1-3) derivatives as potential bidentate ligands, under an unusual kappa(1)-N-coordination mode are reported. All compounds were obtained straightforwardly via reaction of corresponding LPB1-3 and [Pt(Cl)(2)(DMSO)(2)] (DMSO = dimethyl sulfoxide), at 100 degrees C in acetonitrile, respectively. 1-3 complexes were characterized by analytical and spectroscopic data: melting point, FT-IR, Raman, UV/Vis and NMR experiments. Cyclic voltammetry studies show an irreversible two-electron process at -0.50 and -0.51 V, which was ascribed to the Pt(II)/Pt(IV) couple, for complexes 2 and 3. The crystal structure of complex 2 was elucidated by single-crystal X-ray diffraction, where the platinum atom exhibits a square plane geometry, where L-PB2 adopts an unusual mono-coordinated mode via an N-kappa(1)-benzoxazole ring. According to DFT calculations the first N-coordination exchanging one DMSO molecule is favourable, while the second N-coordination is highly impeded.