Synthesis, Structure, and Reactivity of Triosmium Clusters Bearing a Metalated Dialkyl-substituted Pyrazine Ligand

IF 0.4 4区化学 Q4 CRYSTALLOGRAPHY

Journal of Chemical Crystallography Pub Date : 2022-09-05 DOI:10.1007/s10870-022-00958-w

Md. Mahbub Alam, Fahima Islam, Subas Rajbangshi, Kazi A. Azam, Shishir Ghosh, Vladimir N. Nesterov, Michael G. Richmond, Shariff E. Kabir

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引用次数: 0

Abstract

Reactions of two dialkyl-substituted pyrazine ligands with a triosmium cluster are described. Both 2-ethyl-3-methylpyrazine (C₄H₂N₂MeEt) and 2,5-dimethylpyrazine (C₄H₂N₂Me₂) react with the labile triosmium cluster [Os₃(CO)₁₀(NCMe)₂] at 80 °C to afford [HOs₃(CO)₁₀(µ-C₄HN₂MeEt)] (1) and [HOs₃(CO)₁₀(µ-C₄HN₂Me₂)] (2), respectively. Clusters 1 and 2 are formed via C–H bond activation at the α-carbon of the corresponding pyrazine ligand. Cluster 2 reacts with PPh₃ at room temperature in the presence of Me₃NO‧2H₂O to yield the mono- and diphosphine-substituted clusters [HOs₃(CO)₉(PPh₃)(µ-C₄HN₂Me₂)] (3) and [HOs₃(CO)₈(PPh₃)₂(µ-C₄HN₂Me₂)] (4), respectively, both of which exist in more than one isomeric form in solution. All new clusters have been characterized using spectroscopic methods together with single-crystal X-ray diffraction studies for 1, 2, and 4. The bonding in these clusters have been investigated by electronic structure calculations.

Graphical Abstract

Two new triosmium clusters bearing a metalated pyrazine ligand have been synthesized and structurally characterized. The reactivity of one of these newly synthesized clusters towards PPh₃ has also been investigated.

Abstract Image

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含金属化二烷基取代吡嗪配体的三锇簇的合成、结构和反应性

描述了两种二烷基取代吡嗪配体与三锇簇的反应。2-乙基-3-甲基吡嗪(C4H2N2MeEt)和2,5-二甲基吡嗪(C4H2N2Me2)在80℃下与不稳定的三聚氰铵簇[Os3(CO)10(NCMe)2]反应，分别生成[HOs3(CO)10(µ-C4HN2MeEt)](1)和[HOs3(CO)10(µ-C4HN2Me2)](2)。簇1和簇2是通过相应吡嗪配体α-碳上的C-H键活化形成的。簇2在Me3NO·2H2O存在下与PPh3在室温下反应，分别生成单膦和二膦取代簇[HOs3(CO)9(PPh3)(µ- c4hn2me2)](3)和[HOs3(CO)8(PPh3)2(µ- c4hn2me2)](4)，两者在溶液中以不止一种异构形式存在。所有的新团簇都使用光谱方法和单晶x射线衍射研究来表征1、2和4。通过电子结构计算研究了这些团簇中的键合。摘要合成了两个新的含金属化吡嗪配体的三锇簇，并对其进行了结构表征。研究了其中一种新合成的簇对PPh3的反应性。

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来源期刊

Journal of Chemical Crystallography 化学-光谱学

CiteScore

1.50

自引率

12.50%

发文量

审稿时长

6.3 months

期刊介绍： Journal of Chemical Crystallography is an international and interdisciplinary publication dedicated to the rapid dissemination of research results in the general areas of crystallography and spectroscopy. Timely research reports detail topics in crystal chemistry and physics and their relation to problems of molecular structure; structural studies of solids, liquids, gases, and solutions involving spectroscopic, spectrometric, X-ray, and electron and neutron diffraction; and theoretical studies.