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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

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journal contribution
posted on 17.01.2020 by Axel Schulz, Max Thomas, Alexander Villinger
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.