Two heterocyclic cyclopentadienyl analogs with a CB2N2 skeleton, 4-methyl-1,2,3,5-tetraphenyl-1,2-diaza-3,5-diborolidine and 4-methyl-3,5-dimethylamino-1,2-diphenyl-1,2-diaza-3,5-diborolidine were prepared through cyclocondensation of the corresponding 1,1-bis(organochloroboryl)ethane with 1,2-diphenylhydrazine. The former diazadiborolidine featured a cyclopentadiene-like structure with short B-N bonds and a planar ring framework, while in the latter the B-N bonds were noticeably longer and the ring framework was considerably folded as a result of the interaction between boron and the electron donating NMe2 groups. The dimethylamino substituted diazadiborolidine could not be deprotonated due to the reduced acidity of the ring proton, however, the B-phenylated analog was easily deprotonated and the lithium, sodium and potassium 1,2-diaza-3,5-diborolyls were isolated and structurally characterized. The solid state structures of the lithium and sodium salts were similar, with an eta(1)-coordinated pi ligand and three THF molecules completing the coordination sphere of the metal. The potassium salt featured a highly unusual mono-dimensional polymeric structure with the metal pi-coordinated by the CB2N2 ligand and two of the phenyl groups on boron and nitrogen, and sigma-coordinated by one THF molecule.