Zhao Minggang, Xue Tingting, He Ru-Ru, Ma Jianping, Zheng Wenjun
Key Laboratory of Magnetic Molecules & Magnetic Information Materials Ministry of Education, The School of Chemical and Material Science, Shanxi Normal University, Taiyuan, Shanxi 030035, China.
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, Jinan, Shandong 250014, China.
Dalton Trans. 2022 Jan 25;51(4):1634-1645. doi: 10.1039/d1dt03601g.
In this work, eight alkali metal complexes with 1,2-diaza-4-phospholide ligands were prepared and characterized by X-ray single-crystal structural analysis and NMR spectroscopy. Their structures showed varied coordination motifs: (i) a dimeric 1,2-diaza-4-phospholide lithium complex with -bidentate bridging coordination (4) consists of two lithium atoms that are linked two μ-bridging, κ,κ-coordinated ligands; (ii) the polymeric chain 1,2-diaza-4-phospholide potassium complex (5) showed an ion-bearing stair-shaped chain structure running through axis , where the steps are η interactions, and there is a transition platform between every two stairs; (iii) the polymeric chain 1,2-diaza-4-phospholide potassium complex (6) also presented a polymeric chain structure in the solid state but displayed a head-to-tail arrangement of two 1,2-diaza-4-phospholides; (iv) in comparison to 6, the 1,2-diaza-4-phospholide sodium complex (7) displayed a tetrameric structure, in which the sodium ions are arranged in a distorted tetrahedral fashion and each of them occupies a vertex of the tetrahedron; (v) the polymeric chain 1,2-diaza-4-phospholide potassium complex (8) presented a solvent-free chain structure, in which potassium ions each is η-bonded by two 1,2-diaza-4-phospholides and η-coordinated by another, consisting of a stair-shaped chain structure running through axis but without significant intermolecular contacts between the adjacent stairs in comparison to that of 5; (vi) the polymeric chain 1,2-diaza-4-phospholide sodium complex (9) presented a solvent-free chain structure, in which sodium ions each is η(),η(,),η()-bonded by three 1,2-diaza-4-phospholides, consisting of a chain structure running through axis ; and (vii) the treatment complex 8 with elemental sulphur or selenium in the presence of crown ether gave rare thiophosphonato potassium [η(,,)-3,5-Budp-(μ-K)(S)([18]crown-6)] (10) or a selenophosphonato potassium [η(,,)-3,5-Budp-(μ-K)(Se)([18]crown-6)] (11). Both of the complexes crystallized in the orthorhombic space group as pale-yellow (or red) crystals. The X-ray diffraction analysis revealed 10 or 11 as a terminal complex with the η,η-,-coordination mode (X = S and Se). The H DOSY NMR spectroscopy study of the species 8 in DMSO- suggested that polymeric complexes (4-9) in the solid state should dissociate into the related monomers in the solutions when the donor solvents were used.
在本工作中，制备了8种含1,2 - 二氮杂 - 4 - 磷杂环戊二烯配体的碱金属配合物，并通过X射线单晶结构分析和核磁共振光谱对其进行了表征。它们的结构呈现出不同的配位模式：(i) 一种具有双齿桥联配位的二聚1,2 - 二氮杂 - 4 - 磷杂环戊二烯锂配合物 (4) 由两个锂原子组成，这两个锂原子通过两个μ - 桥联、κ,κ - 配位的配体相连；(ii) 聚合物链状1,2 - 二氮杂 - 4 - 磷杂环戊二烯钾配合物 (5) 呈现出沿轴贯穿的含离子阶梯状链结构，其中阶梯为η相互作用，且每两个阶梯之间有一个过渡平台；(iii) 聚合物链状1,2 - 二氮杂 - 4 - 磷杂环戊二烯钾配合物 (6) 在固态时也呈现出聚合物链结构，但两个1,2 - 二氮杂 - 4 - 磷杂环戊二烯呈头对尾排列；(iv) 与6相比，1,2 - 二氮杂 - 4 - 磷杂环戊二烯钠配合物 (7) 呈现出四聚体结构，其中钠离子以扭曲的四面体方式排列，且每个钠离子占据四面体的一个顶点；(v) 聚合物链状1,2 - 二氮杂 - 4 - 磷杂环戊二烯钾配合物 (8) 呈现出无溶剂链结构，其中钾离子各自通过两个1,2 - 二氮杂 - 4 - 磷杂环戊二烯进行η键合，并通过另一个进行η配位，由沿轴贯穿的阶梯状链结构组成，但与5相比，相邻阶梯之间没有明显的分子间接触；(vi) 聚合物链状1,2 - 二氮杂 - 4 - 磷杂环戊二烯钠配合物 (9) 呈现出无溶剂链结构，其中钠离子各自通过三个1,2 - 二氮杂 - 4 - 磷杂环戊二烯进行η( )、η(, )、η(, )键合，由沿轴贯穿的链结构组成；(vii) 在冠醚存在下，用元素硫或硒处理配合物8得到了罕见的硫代膦酸根合钾 [η(,,)-3,5 - Budp-(μ - K)(S)([18]冠 - 6)] (10) 或硒代膦酸根合钾 [η(,,)-3,5 - Budp-(μ - K)(Se)([18]冠 - 6)] (11)。这两种配合物均以浅黄色（或红色）晶体形式在正交空间群中结晶。X射线衍射分析表明10或11为具有η,η -,-配位模式（X = S和Se）的末端配合物。在DMSO - 中对物种8进行的H DOSY NMR光谱研究表明，当使用供体溶剂时，固态的聚合物配合物 (4 - 9) 在溶液中应解离为相关的单体。
