Synthesis and Structure of Bismuth-Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ3-N-TMP)]4: A Dimer of a 1,3-Dichloro-cyclo-dibismadiazane.

The reaction of TMP-NH2 [TMP = m,m-(CF3)2-C6H3] with 2 equiv of n-BuLi led to the in situ formation of Li2[N-TMP], which, after the addition of BiCl3, formed a [Cl-Bi(μ3-N-TMP)]4-type heterocubane in up to 30% yield. Transmetalation reactions, thought of as alternatives, starting from the analogous tin-nitrogen heterocubane [Sn(μ3-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 [Cl-Bi(μ3-N-TMP)]4 are highlighted. In an attempt to isolate Li2[N-TMP], generated in situ from TMP-NH2 and 2 equiv of n-BuLi, it was possible to isolate a lithium salt with a negatively charged lithium cluster of the type [Li9(N-TMP)5F]2- with an unusual Li9N5F skeleton.