期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 58, 期 52, 页码 19007-19013出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201910568
关键词
boron clusters; carbanions; carboranes; lithiates; zincates
资金
- Natural Science Foundation of China [21871231, 21702182, 21873081]
- National Basic Research Program of China [2015CB856500]
- Special Funds for Basic Scientific Research of Zhejiang University
The lithiacarborane [Li-CB11H11](-) plays a central role in carborane chemistry, as it is a key intermediate to achieve the selective functionalization of the monocarba-closo-dodecaborate [CB11H12](-) 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 [CB11H11](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.
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