A novel coordination mode of κ 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 (L 1-3 ) derivatives as potential bidentate ligands, under an unusual κ 1 -N-coordination mode are reported. All compounds were obtained straightforwardly via reaction of corresponding L PB1-3 and [Pt(Cl) 2 (DMSO) 2 ] (DMSO = dimethyl sulfoxide), at 100 °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-κ 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.