Girichev Georgiy V, Giricheva Nina I, Khochenkov Alexey E, Sliznev Valery V, Belova Natalya V, Mitzel Norbert W
Ivanovo State University of Chemistry and Technology, Sheremetevsky avenue 7, Ivanovo, 153000, Russia.
Ivanovo State University, Ermaka Street 39, Ivanovo, 153025, Russia.
Chemistry. 2021 Jan 13;27(3):1103-1112. doi: 10.1002/chem.202004010. Epub 2020 Dec 7.
The molecular structures of potassium tetrakis(hexafluoroacetylacetonato)lanthanide(III) complexes [KLn(hfa) ] (Ln=La, Gd, Lu; hfa=C HF O ,) were studied by synchronous gas-phase electron diffraction/mass spectrometry (GED/MS) supported by quantum-chemical (DFT/PBE0) calculations. The compounds sublime congruently and the vapors contain a single molecular species: the heterobinuclear complex [KLn(hfa) ]. All molecules are of C symmetry with the lanthanide atom in the center of an LnO coordination polyhedron, while the potassium atom is coordinated by three ligands with formation of three K-O and three K-F bonds. One hfa ligand is not bonded to the potassium atom. Topological analysis of the electron-density distributions confirmed the existence of ionic-type K-O and K-F bonding. The structures of the free [KLn(hfa) ] molecules are compared with those of the related compounds [KDy(hfa) ] and [KEr(hfa) ] in their crystalline state. The complex nature of the chemical bonding is discussed on the basis of electron-density topology analyses.
采用量子化学（DFT/PBE0）计算辅助的同步气相电子衍射/质谱法（GED/MS）研究了四（六氟乙酰丙酮）镧系元素（III）酸钾配合物[KLn（hfa）₄]（Ln = La、Gd、Lu；hfa = C₅HF₂O₂⁻）的分子结构。这些化合物能完全升华，其蒸气包含单一分子物种：异双核配合物[KLn（hfa）₄]。所有分子都具有C₃对称性，镧系原子位于LnO₉配位多面体的中心，而钾原子由三个配体配位，形成三个K - O键和三个K - F键。一个hfa配体不与钾原子键合。电子密度分布的拓扑分析证实了离子型K - O键和K - F键的存在。将游离的[KLn（hfa）₄]分子结构与相关化合物[KDy（hfa）₄]和[KEr（hfa）₄]在晶体状态下的结构进行了比较。基于电子密度拓扑分析讨论了化学键的复杂性质。
