Nicasio-Collazo Juan, Ramírez-García Gonzalo, Flores-Álamo Marcos, Gutiérrez-Granados Silvia, Peralta-Hernández Juan M, Maldonado José Luis, Jimenez-Halla J Oscar C, Serrano Oracio
Departamento de Química, Universidad de Guanajuato Cerro de La Venada S/N CP 36040 Guanajuato Gto Mexico
Research Group of Optical Properties of Materials (GPOM), Centro de Investigaciones en Óptica AP 37000 León Guanajuato Mexico
RSC Adv. 2019 May 7;9(25):14033-14039. doi: 10.1039/c9ra01856e.
Herein, three novel Pt(ii) complexes with formula [-Pt(Br-PyBenz-X)(Cl)(DMSO)] (1-3) having Br-pyridylbenz-(imida, oxa or othia)-zole (L) derivatives as potential bidentate ligands, under an unusual κ-N-coordination mode are reported. All compounds were obtained straightforwardly reaction of corresponding L and [Pt(Cl)(DMSO)] (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 adopts an unusual mono-coordinated mode an N-κ-benzoxazole ring. According to DFT calculations the first N-coordination exchanging one DMSO molecule is favourable, while the second N-coordination is highly impeded.
在此，报道了三种新型的分子式为[-Pt(Br-PyBenz-X)(Cl)(DMSO)]（1 - 3）的铂（II）配合物，其具有Br - 吡啶基苯 -（咪唑、恶唑或硫恶唑）- 唑（L）衍生物作为潜在的双齿配体，处于一种不寻常的κ - N配位模式。所有化合物分别通过相应的L与[Pt(Cl)(DMSO)]（DMSO = 二甲基亚砜）在100°C的乙腈中直接反应制得。通过分析和光谱数据对1 - 3配合物进行了表征：熔点、傅里叶变换红外光谱、拉曼光谱、紫外/可见光谱和核磁共振实验。循环伏安法研究表明，配合物2和3在 - 0.50和 - 0.51 V处有一个不可逆的双电子过程，这归因于Pt（II）/Pt（IV）电对。通过单晶X射线衍射阐明了配合物2的晶体结构，其中铂原子呈现平面正方形几何构型，其中L采用一种不寻常的单配位模式，即与一个N - κ - 苯并恶唑环配位。根据密度泛函理论计算，第一次N配位交换一个DMSO分子是有利的，而第二次N配位则受到高度阻碍。
