Ruthenium(II) complexes of a tripodal phosphite ligand: Synthesis, characterization, and applications in catalytic dehydrogenation

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2024-08-14 DOI:10.1016/j.ica.2024.122314

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Abstract

The scaffold tris(8-quinolinyl)phosphite, (P(Oquin)₃), can bind to metal centers as a bi- or a tridentate tripodal ligand, depending on the synthetic conditions and characteristics of the metal atom. Here the study of the coordinating properties of such chelate was extended to the synthesis and characterization of well-defined Ru(II)-halide complexes. The compound [κ³(N,P,N){P(Oquin)₃}RuCl₂(PPh₃)] was obtained by simple ligand exchange on the precursor [(PPh₃)₃RuCl₂]. Two isomers were observed by means of ³¹P{¹H} NMR spectroscopy, and were partially separated by recrystallization in refluxing solvents, thus allowing their structure elucidation. X-ray diffraction analysis revealed that the two crystalline isomers have the formula [κ³(N,P,N){P(Oquin)₃}RuCl₂(PPh₃)] with the phosphite ligand coordinated to the Ru(II) center either in a meridional or in a facial disposition. The mixture [κ³(N,P,N){P(Oquin)₃}RuCl₂(PPh₃)] undergoes phosphine dissociation at temperatures over 100 °C, leading to the formation of [κ⁴(P,N₃){P(Oquin)₃}RuCl₂]. This compound displays a tetradentate P(Oquin)₃ chelate and is a suitable catalyst for the dehydrogenation of formic acid and the dehydrocoupling of methylphenylsilane.

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三重亚磷酸配体的钌（II）配合物：合成、表征及在催化脱氢中的应用

根据合成条件和金属原子的特性，三（8-喹啉基）亚磷酸酯（P(Oquin)3）支架可以作为双或三叉三联配体与金属中心结合。在这里，对这种螯合物配位特性的研究扩展到了明确定义的 Ru(II)- 卤化物配合物的合成和表征。化合物 [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)]是通过对前体 [(PPh3)3RuCl2]进行简单的配体交换而得到的。通过 31P{1H} NMR 光谱法观察到了两种异构体。通过在回流溶剂中重结晶，部分分离出了两种异构体，从而使它们的结构得以阐明。X 射线衍射分析表明，这两种晶体异构体的结构式为 [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)]，亚磷酸配体与 Ru(II) 中心的配位方式为经向或面向。混合物[κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)]在温度超过 100 °C 时会发生膦解离，从而形成[κ4(P,N3){P(Oquin)3}RuCl2]。这种化合物显示出四价 P(Oquin)3 螯合作用，是甲酸脱氢和甲基苯基硅烷脱氢偶联的合适催化剂。

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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.