A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB₁₁H₁₁]⁻

Abstract

The lithiacarborane [LiÀCB 11 H 11 ] À playsacentral role in carborane chemistry,a si ti sakey intermediate to achieve the selective functionalization of the monocarba-closododecaborate [CB 11 H 12 ] À for applications in various fields. Also,i ti sa no rganometallic species of fundamental interest because it represents a3Danalogue of phenyllithium featuring an exo CÀLi 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 [CB 11 H 11 ] 2À has been isolated as its lithiate as well as zincate in pure form and fully characterized.D FT calculations corroborate the experimental findings and underscore the remarkably high reactivity of the lithiacarborane.S ubsequent derivatizations demonstrate the relevance of its initial clean formation.