A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB 11 H 11 ] −
| Autor: | Tian-Cheng Zhu, Yunjun Shen, Rakesh Dontha, Simon Duttwyler, Xin Hong, Michael Wörle |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
010405 organic chemistry
General Medicine General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry.chemical_compound Delocalized electron Chemical bond chemistry Computational chemistry Carborane Reactivity (chemistry) Phenyllithium Carbanion Zincate Group 2 organometallic chemistry |
| Zdroj: | Angewandte Chemie International Edition. 58:19007-19013 |
| ISSN: | 1521-3773 1433-7851 |
| DOI: | 10.1002/anie.201910568 |
| Popis: | The lithiacarborane [Li-CB11 H11 ]- plays a central role in carborane chemistry, as it is a key intermediate to achieve the selective functionalization of the monocarba-closo-dodecaborate [CB11 H12 ]- for applications in various fields. Also, it is an organometallic species of fundamental interest because it represents a 3D analogue of phenyllithium featuring an exo C-Li bond in addition to the delocalized negative endo charge of the spherical cluster. For the first time, the elusive and highly reactive endo/exo formal dianion [CB11 H11 ]2- has been isolated as its lithiate as well as zincate in pure form and fully characterized. DFT calculations corroborate the experimental findings and underscore the remarkably high reactivity of the lithiacarborane. Subsequent derivatizations demonstrate the relevance of its initial clean formation. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Plný text