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

Author(s) Schulz, A.; Thomas, M.; Villinger, A.
Journal Inorg Chem
Date Published 2020 Jan 17
Abstract

The reaction of TMP-NH [TMP = ,-(CF)-CH] with 2 equiv of -BuLi led to the in situ formation of Li[N-TMP], which, after the addition of BiCl, formed a [Cl-Bi(μ-N-TMP)]-type heterocubane in up to 30% yield. Transmetalation reactions, thought of as alternatives, starting from the analogous tin-nitrogen heterocubane [Sn(μ-N-TMP)] and BiCl 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(μ-N-TMP)] are highlighted. In an attempt to isolate Li[N-TMP], generated in situ from TMP-NH and 2 equiv of -BuLi, it was possible to isolate a lithium salt with a negatively charged lithium cluster of the type [Li(N-TMP)F] with an unusual LiNF skeleton.

DOI 10.1021/acs.inorgchem.9b03221
ISSN 1520-510X
Citation Schulz A, Thomas M, Villinger A. Synthesis and Structure of Bismuth-Nitrogen Cage Compounds and Heterocubanes: [Cl-Bi(μ-N-TMP)]: A Dimer of a 1,3-Dichloro--dibismadiazane. Inorg Chem. 2020.