金属炔化物配合物（M = Li, Na, Ca, Zn）的配体

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-05-08 DOI:10.1021/acs.inorgchem.5c01178

Na Zhang, Li Wu, Yujie Jin, Kang Zhang, Jiyong Liu, Simon Duttwyler

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引用次数: 0

摘要

我们报道了基于单碳硼烷内/外重阴离子框架[CB11H11-12-C≡C]2 -首次分离出含锂、钠、钙和锌的金属炔化物配合物（2a-d）。这些配合物是通过末端炔的去质子化合成的，并使用锂、钠、钙和锌等六甲基二叠氮化碱进行优化，以提高收率和晶体稳定性。x射线晶体学和核磁共振光谱显示了独特的配位几何，包括2a中罕见的椅子形Li4C2O2单元，2b-c中的多核单元和2d中的六边形Zn3C3单元。随后与二苯甲酮的亲核反应产生了高效的丙炔醇(3)，证明了它们在复杂分子组装的选择性合成路线上的实用性。这项工作不仅突出了碱金属和碱土金属在单碳硼烷金属乙酰醚中的反应性，而且为其结构特征和在先进材料和催化体系中的潜在应用提供了有价值的见解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

The 12-Ethynylmonocarba-closo-dodecaborate Anion: A Ligand for Metal Alkynide Complexes (M = Li, Na, Ca, Zn)

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The 12-Ethynylmonocarba-closo-dodecaborate Anion: A Ligand for Metal Alkynide Complexes (M = Li, Na, Ca, Zn)

We report the first isolation of metal alkynide complexes (2a-d) incorporating lithium, sodium, calcium and zinc based on the monocarborane endo/exo-dianionic framework [CB₁₁H₁₁-12-C≡C]^2–. These complexes are synthesized via the deprotonation of terminal alkynes and optimized using lithium, sodium, calcium, and zinc hexamethyldisilazide bases to achieve enhanced yields and crystal stability. X-ray crystallography and NMR spectroscopy reveal unique coordination geometries, including a rare chair-shaped Li₄C₂O₂ unit in 2a, multinuclear units in 2b–c, and a hexagonal Zn₃C₃ unit in 2d. Subsequent nucleophilic reactions with benzophenone afford propargylic alcohols (3) with high efficiency, demonstrating their utility in selective synthetic routes for complex molecular assembly. This work not only highlights the reactivity of alkali and alkaline-earth metals in monocarborane metal acetylides but also offers valuable insights into their structural characteristics and potential applications in advanced materials and catalytic systems.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.