The bis(trimethylsilyl)amide ligand, [N(SiMe3)2]-,has proven to be a useful ancillary ligand in molecular rare earth chemistry. It has been the supporting ligand for an extensive series of reduced dinitrogen complexes containing (N2)2- bridging moieties, {[(Me3Si)2N]2(THF)Ln}2(�-?2:?2-N2) (Ln = Y, lanthanides), which have led to the first examples of the (N2)3- and (NO)2- radical ions as well as single-molecule magnets (SMMs) with the highest blocking temperatures to date, namely {[(Me3Si)2N]2(THF)Ln}2(�-?2:?2-N2)[K(18-crown-6)(THF)2] when Ln = Tb, Dy. Reactivity studies of the amide-ligated (N2)2- complexes have now been extended to the chalcogens, and the resulting complexes of reduced sulfur and selenium will be described as well as an unusual co-crystallization of (S2)2- and S2- species. In the course of manipulating these [N(SiMe3)2]- complexes, Nd2Fe13B magnets have been used to generate magnetic fields in the crystallization vessels to study their effect on crystal formation. The utility of this crystallization method will be discussed.

Crystallization and chalcogen reactivity studies of bimetallic rare earth reduced dinitrogen complexes supported by bis(trimethylsilyl)amide ancillary ligands

248th National Meeting (2014)

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