Abstract Two new nickel phosphor-1,1-dichalcogenide complexes were synthesized from the reaction between Ni(II) salt and diselenophosphonate and dithiophosphonate ligands, forming complexes [Ni{Se2PPh(OEt)}2] 1 and [Ni{S2P(4-C6H4OMe) (OCH(CH2CH3)2}2] 2, respectively. Complexes 1 and 2 were fully characterized by single-crystal X-ray diffraction, 1H and 31P NMR spectroscopy, electrospray ionization mass spectrometry, and elemental analysis. Both complexes crystallized in the triclinic P-1 space group and adopted a square planar geometry around the central Ni atom which was also positioned on a crystallographic inversion centre. The bond lengths of Ni–Se in 1 was on average 2.34 A whilst for Ni–S in 2 unsurprisingly shorter in the range 2.21–2.23 A. Complexes 1 and 2 has the same metal centre, and similar geometries, coordination modes and ligand types, differing only in chalcogenide donor atom binding to the metal, making 1 and 2 good candidates for theoretical studies and comparisons with experimental results. Density functional theory (DFT) was utilized to explain the structural and electronic properties of complexes. The DFT calculations employed B3LYP functional with 6-31 + G (d,p) basis set for ligand atoms and LANL2DZ for the central metal ions to obtain an optimized geometrical structure, and to perform an electronic and natural bond orbital (NBO) analysis.

中文翻译：

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来自磷-二硫属化物（P/Se2 和 P/S2）型配体的镍 (II) 配合物：合成、结构和理论计算

配位模式和配体类型，仅在硫属化物供体原子与金属结合方面有所不同，使 1 和 2 成为理论研究和与实验结果比较的良好候选者。密度泛函理论（DFT）被用来解释配合物的结构和电子特性。DFT 计算采用 B3LYP 泛函，配体原子采用 6-31 + G (d,p) 基组，中心金属离子采用 LANL2DZ，以获得优化的几何结构，并进行电子和自然键轨道 (NBO) 分析。