Synthesis and structural characterization of mono- and bimetallic azodioxide complexes of first-series transition metals

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Inorganica Chimica Acta Pub Date : 2024-08-31 DOI:10.1016/j.ica.2024.122354

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Abstract

The treatment of metal chlorides MCl₂ or metal chlorido complexes M(bpy)Cl₂ (M = Mn, Ni, Cu, bpy = 2,2′-bipyridyl) with TlPF₆ in acetonitrile to precipitate TlCl, followed by addition of excess nitrosobenzene, yielded monometallic or bimetallic azodioxide complex salts of the form [M(az)₄](PF₆)₂, [M(bpy)₂(az)](PF₆)₂, and [{M(bpy)(az)(μ-Cl)}₂](PF₆)₂ (az = cis-N,N′-diphenylazodioxide), which have been structurally characterized via single-crystal X-ray diffraction. The method of activation of chloride salts or chlorido complexes by chloride abstraction with Tl⁺, followed by the addition of nitrosobenzene, continues to be an effective strategy for the synthesis of azodioxide complexes, and it has enabled the synthesis of the first structurally characterized azodioxide complexes of any metals of Groups 7, 10, or 11.

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第一系过渡金属的单金属和双金属叠氮二氧化物配合物的合成与结构表征

在乙腈中用 TlPF6 处理金属氯化物 MCl2 或金属氯络合物 M(mby)Cl2（M = Mn、Ni、Cu，mby = 2,2′-联吡啶）以沉淀 TlCl，然后加入过量亚硝基苯、得到了[M(az)4](PF6)2、[M(bpy)2(az)](PF6)2 和[{M(bpy)(az)(μ-Cl)}2](PF6)2（az = 顺式-N,N′-二苯基二氧化氮）形式的单金属或双金属偶氮二氧化物复盐，这些复盐已通过单晶 X 射线衍射获得结构特征。先用 Tl+ 抽取氯化物活化氯盐或氯化物络合物，然后加入亚硝基苯的方法仍然是合成氮氧化物络合物的有效策略，而且这种方法首次合成了具有结构特征的第 7、10 或 11 族金属的氮氧化物络合物。

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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.