The reaction of bismuth amides or alkoxides with phenolic ligand precursors yields Bi complexes of aminetris( phenoxide) s, one of which was characterized by X-ray crystallography, revealing monomeric Bi units of the tetradentate NO3 ligand further associated via a symmetrical toluene bridge into a bis( bismuth) toluene inverted-sandwich complex. Synthesis of the analogous Sb complex suggests a markedly different geometric and electronic environment at the metal center, as evidenced by the solid-state molecular structure. Density functional theory calculations of the sandwich bismuth arene complex indicate the presence of a weak sigma(*)-2 pi interaction.