Stabilization of the Elusive 9‐Carbene‐9‐Borafluorene Monoanion
Kelsie E. Wentz, Andrew Molino, Sarah L. Weisflog, Aishvaryadeep Kaur, Diane A. Dickie, David J. Wilson, Robert J. Gilliard
Abstract
, Na, or Li-naphthalenide affords six N-heterocyclic carbene (NHC)- or cyclic(alkyl)(amino) carbene (CAAC)-stabilized borafluorene anions (3-8)-the first isolated and structurally authenticated examples of the elusive 9-carbene-9-borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B-E (E=Au, Se, Ge)-containing materials (9-12). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B-O containing spirocycles (13-14) that cannot be easily obtained using "normal" valent borafluorene compounds. Collectively, these results support the notion that carbene-stabilized monoanionic borafluorenes may serve as a new platform for the one-step construction of higher-value boracyclic materials.