The reactivity of the 2‐chloroazaborolyl anion (LBCl)[K(THF)] {1; L = [ArNC(R)CHC(R)]–; Ar = 2,6‐Me2C6H3, R = tBu} was investigated. Treatment of 1 with a diazomethane resulted in the formation of a donor‐stabilized iminoborane featuring an intramolecular donor‐stabilized B=N bond. Compound 1 readily reacted with chlorotriphenyltin to afford the new 1,2‐azaborolyl complex 3, whereas reactions with ortho‐quinone, azobenzene, and diphenyl disulfide led to the oxidative cycloaddition and cleavage of the disulfide S–S bond, with elimination of KCl.