A Cationic NHC-Supported Borole

Chemistry. 2020 Sep 10;26(51):11684-11689. doi: 10.1002/chem.202001916. Epub 2020 Aug 13.

Abstract

This work describes the synthesis and characterization of a highly reactive cationic borole. Halide abstraction with Li{Al[OC(CF3 )3 ]4 } from the NHC-chloroborole adduct yields the first stable NHC-supported 1-(Me NHC)-2,5-(SiMe3 )2 -3,4-(Ph*)2 -borole cation. Electronically, it features both a five-membered cyclic conjugated 4 π-electron system and a cationic charge and thus resembles the yet elusive cyclopentadienyl cation. The borole cation was characterized crystallographically, spectroscopically (NMR, UV/Vis), by cyclovoltammetry, microanalysis and mass-spectrometry and its electronic structure was probed computationally. The cation reacts with tolane and reversibly binds carbon monoxide. Direct comparison with the structurally related, yet neutral, 1-mesityl borole reveals strong Lewis acidity, reduced HOMO-LUMO gaps, and increased anti-aromatic character.

Keywords: CO-complex; borenium cation; boroles; maingroup heterocycles.