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

2019; Royal Society of Chemistry; Volume: 9; Issue: 25 Linguagem: Inglês

10.1039/c9ra01856e

2046-2069

Juan Nicasio‐Collazo, Gonzalo Ramírez‐García, Marcos Flores‐Álamo, Silvia Gutiérrez‐Granados, Juan M. Peralta‐Hernández, José‐Luis Maldonado, J. Óscar C. Jiménez‐Halla, Oracio Serrano,

Magnetism in coordination complexes

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.