A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB11H11]−. Issue 52 (11th November 2019)

• Record Type: Journal Article
• Authors: Dontha, Rakesh; Zhu, Tian‐Cheng; Shen, Yunjun; Wörle, Michael; Hong, Xin; Duttwyler, Simon
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 52(2019)
• Page Start: 19007
• Page End: 19013
• Publication Date: 2019-11-11
• Subjects: boron clusters -- carbanions -- carboranes -- lithiates -- zincates; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201910568
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: 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. Abstract : Analogical 3D extension : The lithiacarborane [Li−CB11 H11 ] − plays a central role in carborane chemistry and is an organometallic species of fundamental interest because it represents a 3D analogue of phenyllithium featuring an exo C−Li bond as well as a spherically delocalized negative endo charge. The high‐yield isolation and detailed structural characterization of the lithiate and zincate are presented alongside DFT calculations.