Isolation of Stable Borepin Radicals and Anions

Borepin, a 7-membered boron-containing heterocycle, has become an emerging molecular platform for the development of new materials and optoelectronics. While electron-deficient borepins are well-established, reduced electron-rich species have remained elusive. Herein we report the first isolable, crystalline borepin radical (2 a, 2 b) and anion (3 a, 3 b) complexes, which have been synthesized by potassium graphite (KC8) reduction of cyclic(alkyl)(amino) carbene-dibenzo[b,d]borepin precursors. Borepin radicals and anions have been characterized by EPR or NMR, elemental analysis, X-ray crystallography, and cyclic voltammetry. In addition, the bonding features have been investigated computationally using density functional theory.