Heterometallic Ru–Ir Hydride Carbonyl Clusters

IF 2.7 4区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Cluster Science Pub Date : 2024-12-02 DOI:10.1007/s10876-024-02723-9

Francesca Forti, Cristiana Cesari, Marco Bortoluzzi, Cristina Femoni, Tiziana Funaioli, Maria Carmela Iapalucci, Stefano Zacchini

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Abstract

[NEt₄][Ru₃(µ-H)(µ-CO)(CO)₁₀] (1) reacts with [{Ir(µ-Cl)(cod)}₂] in a 1 : 0.5 molar ratio under H₂ atmosphere affording the previously reported [NEt₄][Ru₃Ir(µ-H)₂(µ-CO)₃(CO)₉] (2). Performing the reaction under N₂ atmosphere with a 1 : 1 molar ratio of the reagents results in the new species [NEt₄][Ru_3–xIr_2+x(μ-H)_1–x(µ_3-CO)(µ-CO)₃(CO)₈(cod)] (x = 0.11) (3), whereas [Ru_3−xIr_2+x(µ-H)_2–x(µ-CO)₄(CO)₆(cod)₂] (x = 0.5 and 0.77) (4) is obtained by further increasing the amount of [{Ir(µ-Cl)(cod)}₂]. In particular, compound 4 with x = 0.5 has been obtained with a 1:1.25 molar ratio of the reagents, whereas 4 with x = 0.77 is formed increasing the stoichiometry to 1:1.5. Reaction of 1 and [{Ir(µ-Cl)(cod)}₂] under CO atmosphere affords [NEt₄]₂[Ru₄Ir₂(µ-CO)₅(CO)₁₂] (5) (molar ratio of the reagents 1:0.7). Syntheses of 2-5 are very sensitive to the experimental conditions, and optimized procedures in order to obtain each of these compounds in good yield and high purity have been identified. Slight variations of the experimental conditions lead to lower yield and traces of side-products are formed, among which [NEt₄][Ru₃Ir(µ-H)₂(µ-CO)₃(CO)₇(cod)] (6), [NEt₄][Ru₃Ir(µ-H)(µ-Cl)(µ-CO)₃(CO)₉] (7), [NEt₄]₃[Ru₂Ir₂(µ₃-H)(µ-CO)₃(CO)₉]Cl₂ (8) and [NEt₄]₂[Ru₄(µ₄-O)(µ-Cl)₄(µ-CO)₂(CO)₈] (9) have been identified by single-crystal X-ray diffraction (SC-XRD). All the main products 2-5 have been structurally characterized by SC-XRD and further investigated by IR and ¹H NMR spectroscopy in solution. Hydride locations have been elucidated by computational methods.

Graphical Abstract

Homoleptic and heteroleptic heterometallic Ru-Ir hydride carbonyl clusters have been obtained from [NEt4][Ru3(µ-H)(µ-CO)(CO)10] and [Ir(COD)Cl]2 under different experimental conditions.

Abstract Image

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异质金属Ru-Ir氢化物羰基簇

[NEt4] [Ru3(µ- h)(µ有限公司)(CO) 10](1)反应[{红外(µcl) (cod)} 2] 1: 0.5克分子比下H2气氛提供之前报道[NEt4] [Ru3Ir(µ- h) 2(µCO) 3 (CO) 9](2),执行N2气氛下的反应1:1克分子比试剂结果的新物种[NEt4] [Ru3-xIr2 + x(μ- h) 1 - x(µ3-CO)(µCO) 3 (CO) 8 (cod)] (x = 0.11)(3),而[Ru3−中的xIr2 + x(µ- h) 2 x(µCO) 4 (CO) 6 (cod) 2] (x = 0.5和0.77)(4)通过进一步增加[{红外(µcl) (cod)} 2]。特别是，x = 0.5的化合物4以1:1.25的摩尔比得到，而x = 0.77的化合物4的化学计量比增加到1:1.5。1与[{Ir（µ-Cl）（cod）}2]在CO气氛下反应得到[NEt4]2[Ru4Ir2（µ-CO）5(CO)12](5)（试剂摩尔比1:7 .7）。其中2-5种化合物的合成对实验条件非常敏感，并确定了最佳的合成工艺，以获得产率高、纯度高的化合物。通过单晶x射线衍射（SC-XRD）鉴定出了[NEt4][Ru3Ir（µ-H）2（µ-CO）3(CO)7(cod)](6)、[NEt4][Ru3Ir（µ-H）（µ-Cl）（µ-CO）3(CO)9](7)、[NEt4]3[Ru2Ir2（µ3-H）（µ-CO）3(CO)9]Cl2(8)和[NEt4]2[Ru4（µ4- o）（µ-Cl）4（µ-CO）2(CO)8](9)副产物。所有主要产物2-5都用SC-XRD进行了结构表征，并在溶液中进一步用IR和1H NMR进行了表征。氢化物的位置已通过计算方法加以阐明。摘要以[NEt4][Ru3（µ-H）（µ-CO）（CO）10]和[Ir(COD)Cl]2为原料，在不同的实验条件下，得到了钌-Ir氢化物羰基簇。

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来源期刊

Journal of Cluster Science 化学-无机化学与核化学

CiteScore

6.70

自引率

0.00%

发文量

166

审稿时长

3 months

期刊介绍： The journal publishes the following types of papers: (a) original and important research; (b) authoritative comprehensive reviews or short overviews of topics of current interest; (c) brief but urgent communications on new significant research; and (d) commentaries intended to foster the exchange of innovative or provocative ideas, and to encourage dialogue, amongst researchers working in different cluster disciplines.