The reaction of TMP-NH2 [TMP = m,m-(CF3)(2)-C6H3] with 2 equiv of n-BuLi led to the in situ formation of Li-2 [N-TMP], which, after the addition of BiCl3, formed a [Cl-Bi(mu(3)-N-TMP)](4) type heterocubane in up to 30% yield. Transmetalation reactions, thought of as alternatives, starting from the analogous tin-nitrogen heterocubane [Sn(mu(3)-N-TMP)](4) and BiCl3 resulted in the isolation of a complex reaction mixture from which different Bi-N and Bi-Sn-N cage compounds could be isolated. The structures of all cage compounds that contain bismuth are discussed, and the thermodynamics of the formation of [CI-Bi(mu(3)-N-TMP)](4) are highlighted. In an attempt to isolate Li-2[N-TMP], generated in situ from TMP-NH, and 2 equiv of n-BuLi, it was possible to isolate a lithium salt with a negatively charged lithium cluster of the type [Li-9(N-TMP)(5)F](2-) with an unusual Li9N5F skeleton.