A novel coordination mode of κ1-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 κ1-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 °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 LPB2 adopts an unusual mono-coordinated mode via an N-κ1-benzoxazole ring. According to DFT calculations the first N-coordination exchanging one DMSO molecule is favourable, while the second N-coordination is highly impeded.
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