Osmium and ruthenium carbonyl clusters containing arsine, arsenide, and arsinidene ligands

IF 2.7 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Inorganica Chimica Acta Pub Date : 2024-09-01 DOI:10.1016/j.ica.2024.122351

Md. Nazmul Huda , Md. Abdullah Al Mamun , Md. Sohag Hasan , Vladimir N. Nesterov , Shariff E. Kabir , Shishir Ghosh

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Abstract

The reactivity of trimetallic clusters [Os₃(CO)₁₀(NCMe)₂], [M₃(CO)₁₀(µ-dppm)] [M = Os, Ru; dppm = bis(diphenylphosphino)methane] and [Os₃(CO)₈{µ₃-Ph₂PCH₂PPh(C₆H₄)}(µ-H)] with triphenylarsine (AsPh₃) has been investigated. The labile [Os₃(CO)₁₀(NCMe)₂] reacts with AsPh₃ at room temperature to give 1,2-[Os₃(CO)₁₀(AsPh₃)₂] (1) in good yield. Thermolysis of 1 in refluxing toluene affords the known clusters [Os₃(CO)₁₁(AsPh₃)] (2), [Os₃(CO)₉(µ-AsPh₂)(µ₃,η²-C₆H₄)(µ-H)] (3) and [Os₃(CO)₇(µ-AsPh₂)₂(µ_3,η²-C₆H₄)] (4). Treatment of [Os₃(CO)₁₀(µ-dppm)] with AsPh₃ in refluxing toluene affords [Os₃(CO)₉(AsPh₃)(µ-dppm)] (5) as the major product together with [Os₃(CO)₇(AsPh₃){µ₃-Ph₂PCH₂PPh(C₆H₄)}(µ-H)] (6). Control experiment shows that 5 is a precursor of 6 as the former converts to the latter under similar experimental conditions. The same reaction affords 5 as the sole product when it is carried out in refluxing benzene. Cluster 5 and 6 can also be obtained in similar yield by treating [Os₃(CO)₈{µ₃-Ph₂PCH₂PPh(C₆H₄)}(µ-H)] with AsPh₃ at room temperature. On the other hand, the reaction of [Ru₃(CO)₁₀(µ-dppm)] with AsPh₃ in refluxing toluene furnishes only [Ru₄(CO)₈(µ-CO)(μ₄-AsPh)(µ₄,η²-C₆H₄)(µ-dppm)] (7) in low yield. Cluster 7 can also be obtained by heating [Ru₃(CO)₉(AsPh₃)(µ-dppm)] in refluxing toluene. It contains a phenylarsinidene and a benzyne ligands that were formed by AsC bond cleavage during the reaction. The molecular structures of all the new products have been established by X-ray crystallography.

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含有胂、砷化物和亚胂配体的锇和钌羰基团簇

研究了三金属团簇[Os3(CO)10(NCMe)2]、[M3(CO)10(µ-dppm)][M = Os、Ru；dppm = 双（二苯基膦）甲烷]和[Os3(CO)8{µ3-Ph2PCH2PPh(C6H4)}(µ-H)]与三苯基胂（AsPh3）的反应性。室温下，易溶的[Os3(CO)10(NCMe)2]与 AsPh3 发生反应，生成 1,2-[Os3(CO)10(AsPh3)2]（1），收率很高。将 1 在回流甲苯中热解，可得到已知的簇合物 [Os3(CO)11(AsPh3)] (2)、[Os3(CO)9(µ-AsPh2)(µ3,η2-C6H4)(µ-H)] (3) 和 [Os3(CO)7(µ-AsPh2)2(µ3,η2-C6H4)] (4)。将[Os3(CO)10(µ-dppm)]与 AsPh3 在回流甲苯中进行处理，得到主要产物[Os3(CO)9(AsPh3)(µ-dppm)](5)和[Os3(CO)7(AsPh3){µ3-Ph2PCH2PPh(C6H4)}(µ-H)](6)。对照实验表明，5 是 6 的前体，因为前者会在类似的实验条件下转化为后者。同样的反应在回流苯中进行时，5 是唯一的产物。在室温下用 AsPh3 处理[Os3(CO)8{µ3-Ph2PCH2PPh(C6H4)}(µ-H)]，也能以类似的产率得到簇 5 和簇 6。另一方面，[Ru3(CO)10(µ-dppm)]与 AsPh3 在回流甲苯中反应只得到低产率的[Ru4(CO)8(µ-CO)(μ4-AsPh)(µ4,η2-C6H4)(µ-dppm)]（7）。在回流甲苯中加热[Ru3(CO)9(AsPh3)(µ-dppm)]也可以得到簇 7。它含有一个苯基胂烯配体和一个苄炔配体，这两个配体是在反应过程中通过 AsC 键裂解形成的。所有新产物的分子结构均已通过 X 射线晶体学方法确定。

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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.