Synthesis and isolation of dinuclear N,C-chelate organoboron compounds bridged by neutral, anionic, and dianionic 4,4'-bipyridine reductive coupling of pyridines.

The reaction of Bppy(Mes)2 (BN1; ppy = 2-phenylpyridine) and BCHppy(Mes) (BN3) with the reducing reagent KC resulted in C-C bond formation intermolecular radical coupling to generate the 4,4'-bipyridyl ligand compounds BN2 and BN4. Adding 1 equivalent of KC to a THF solution of BN2 and BN4 generated the 4,4'-bipyridyl radical anions BN2K and BN4K. The dianion species BN2K2 and BN4K2 could be obtained by adding 2 equivalents of KC to the THF solution of BN2 and BN4. In the presence of 2,2,2-cryptand or 18-crown-6, the radical anion salt BN2K(crypt) and the dianion salt BN2K2(18c6)2 were isolated for single-crystal X-ray diffraction analysis. Structural, spectroscopic, and computational studies were performed on the three species of BN2 derivatives (neutral, radical anion, and dianion species). BN2 and BN4 were stable and did not undergo photoisomerization or photoelimination under UV light irradiation.