Structure-constraint induced increase in Lewis acidity of tris(ortho-carboranyl)borane and selective complexation with Bestmann ylides

Abstract

The Lewis acidity of tris(ortho-carboranyl)borane has been slightly increased by mimicking the structural evolution from triarylborane to 9-aryl-9-borafluorene. The o-carborane-based analogue (C2B10H10)2B(C2B10H11), obtained via salt elimination between LiC2B10H11 and (C2B10H10)2BBr, has been fully characterized. Gutmann–Beckett and computational fluoride/hydride ion affinity (FIA/HIA) studies have confirmed the increase in Lewis acidity, which is attributable to structural constraint imposed by the CC-coupling between two carboranyl groups. Selective complexation of (C2B10H10)2B(C2B10H11) with Bestmann ylides R3PCCO (R = Ph, Cy) has been achieved, enabling further conversion into the zwitterionic phospholium salt through NHC-catalyzed proton transfer.