Durán-Carril María L, Fidalgo-Brandón José Ignacio, Lombao-Rodríguez David, Munín-Cruz Paula, Reigosa Francisco, Vila José M
Department of Inorganic Chemistry, University of Santiago de Compostela, E-15782 Santiago de Compostela, Spain.
Molecules. 2024 Sep 4;29(17):4185. doi: 10.3390/molecules29174185.
The electrochemical oxidation of anodic metals (M = nickel and palladium) in an acetonitrile solution of the thiosemicarbazone ligands ()-2-(1-(4-methoxyphenyl)ethylidene)-N-methylhydrazine-1-carbothioamide (a), ()-2-(1-(p-tolyl)ethylidene)hydrazine-1-carbothioamide (b), and ()-N-phenyl-2-(1-(p-tolyl)ethylidene)hydrazine-1-carbothioamide (c) yielded the homoleptic complexes [ML], , , , and and [ML], as air-stable solids. The crystal structures for , , , and show the ligands in a transoid disposition with the [S,S] and [N,N] donor atom pairs occupying positions on the nearly square planar coordination plane of the metal. The structure for of S4 symmetry comprises a tetranuclear palladacycle where the metalated ligands are arranged around a central PdS environment: a crown ring with alternating palladium and sulfur atoms. The latter complex is the first example of an electrochemical preparation of a cyclometalated palladium compound, marking a milestone in the chemistry of such species. The compounds have been fully characterized by elemental microanalysis, mass spectrometry, infrared (IR), and H nuclear magnetic resonance (NMR) spectra.
在硫代氨基脲配体（）-2-（1-（4-甲氧基苯基）亚乙基）-N-甲基肼-1-碳硫酰胺（a）、（）-2-（1-（对甲苯基）亚乙基）肼-1-碳硫酰胺（b）和（）-N-苯基-2-（1-（对甲苯基）亚乙基）肼-1-碳硫酰胺（c）的乙腈溶液中，阳极金属（M = 镍和钯）的电化学氧化产生了同配络合物[ML]、、、和以及[ML]、，它们均为空气稳定的固体。、、和的晶体结构表明，配体呈反式排列，[S,S]和[N,N]供体原子对占据金属近方形平面配位平面上的位置。具有S4对称性的的结构包含一个四核钯环，其中金属化配体围绕中心PdS环境排列：一个由钯和硫原子交替组成的冠环。后一种络合物是环金属化钯化合物电化学制备的首个实例，标志着此类物种化学领域的一个里程碑。这些化合物已通过元素微量分析、质谱、红外（IR）和氢核磁共振（NMR）光谱进行了全面表征。
