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Updated: May 20, 2025

Synthesis of Esters Via a Greener Steglich Esterification in Acetonitrile
Published on: October 30, 2018
The 12-Ethynylmonocarba-closo-dodecaborate Anion: A Ligand for Metal Alkynide Complexes (M = Li, Na, Ca, Zn)
1Shaoxing Key Laboratory of Targeted Drug Delivery and Targeted Materials, Yuanpei College, Shaoxing University, 2799 Qunxian Road, Shaoxing, 312000, China.
Abstract:
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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