Imidobis(tetraphenylphosphinato)lanthanoid(III) complexes: Synthesis by oxidative protolysis, and redox transmetallation/protolysis, structural studies and Hirshfeld surface analysis

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Inorganica Chimica Acta Pub Date : 2024-09-20 DOI:10.1016/j.ica.2024.122385

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Abstract

Redox protolysis of [YbCp₂(dme)] (dme = 1,2-dimethoxyethane) by imidotetraphenyldiphosphinate, ({Ph₂PO}₂NH) LH yields [YbCp{(Ph₂PO)₂N}₂}(MeCN)] 1 and [Yb{(Ph₂PO)₂N}₃] 2 with the last also obtained by oxidative protolysis of Yb(C₆F₅)₂. The complexes [Ln{(Ph₂PO)₂N}₃] ((Ln = Yb 2, Er 3, Gd 4), [Sm{(Ph₂PO)₂N}₃(MeCN)₃] 5 and [Nd{(Ph₂ PO)₂N}₃] 6 have all been prepared by redox transmetallation/protolysis reactions between Yb, Er, Gd, Sm or Nd metals, bispentafluorophenylmercury and proligand LH. Complex 1 is formally eight coordinate with an acetonitrile, cyclopentadienyl (Cp) and two chelating O,O′-(Ph₂PO)₂N ligands, with the MeCN trans to the Cp ring. Complexes 2 and 4·C₇H₈ are six coordinate monomers with three chelating O,O′ diphosphinate ligands. By contrast 5 is a highly symmetrical nine-coordinate monomer with three acetonitrile and three chelating O,O′-L ligands. The three-dimensional Hirshfeld surface (3D-HS) analysis and the two-dimensional fingerprint plots (2D-FP) were quantified for different intermolecular interactions in complexes 2 and 4.

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亚胺双(四苯基膦)镧系(III)配合物：通过氧化原溶解和氧化还原转金属化/原溶解合成、结构研究和 Hirshfeld 表面分析

亚胺四苯基二膦酸盐（{Ph2PO}2NH）LH 对 [YbCp2(dme)] （dme = 1,2-二甲氧基乙烷）的氧化还原原解产生 [YbCp{(Ph2PO)2N}2}(MeCN)] 1 和 [Yb{(Ph2PO)2N}3] 2，最后一种也是通过 Yb(C6F5)2 的氧化原解得到的。[Ln{(Ph2PO)2N}3]（Ln = Yb 2、Er 3、Gd 4）、[Sm{(Ph2PO)2N}3(MeCN)3]5 和[Nd{(Ph2 PO)2N}3] 6 复合物都是通过 Yb、Er、Gd、Sm 或 Nd 金属、双五氟苯基汞和原配体 LH 之间的氧化还原/原分解反应制备的。络合物 1 由乙腈、环戊二烯（Cp）和两个螯合 O，O′-（Ph2PO）2N 配体组成，MeCN 反式连接到 Cp 环上。配合物 2 和 4-C7H8 是六坐标单体，带有三个螯合 O,O′二膦酸配体。相比之下，5 是高度对称的九配位单体，具有三个乙腈配体和三个 O,O′-L螯合配体。对配合物 2 和 4 中不同的分子间相互作用进行了三维 Hirshfeld 表面（3D-HS）分析和二维指纹图谱（2D-FP）量化。

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来源期刊

Inorganica Chimica Acta 化学-无机化学与核化学

CiteScore

6.00

自引率

3.60%

发文量

440

审稿时长

35 days

期刊介绍： Inorganica Chimica Acta is an established international forum for all aspects of advanced Inorganic Chemistry. Original papers of high scientific level and interest are published in the form of Articles and Reviews. Topics covered include: • chemistry of the main group elements and the d- and f-block metals, including the synthesis, characterization and reactivity of coordination, organometallic, biomimetic, supramolecular coordination compounds, including associated computational studies; • synthesis, physico-chemical properties, applications of molecule-based nano-scaled clusters and nanomaterials designed using the principles of coordination chemistry, as well as coordination polymers (CPs), metal-organic frameworks (MOFs), metal-organic polyhedra (MPOs); • reaction mechanisms and physico-chemical investigations computational studies of metalloenzymes and their models; • applications of inorganic compounds, metallodrugs and molecule-based materials. Papers composed primarily of structural reports will typically not be considered for publication.