Straightforward synthesis of rubidium bis(trimethylsilyl)amide and complexes of the alkali metal bis(trimethylsilyl)amides with weakly coordinating 2,2,5,5-tetramethyltetrahydrofuran.

Author(s) Krieck, S.; Schüler, P.; Görls, H.; Westerhausen, M.
Journal Dalton Trans
Date Published 2018 Sep 18

Rubidium bis(trimethylsilyl)amide (rubidium hexamethyldisilazanide, Rb(hmds)) is accessible on a large scale with excellent yields via a magnetite-catalyzed metalation of hexamethyldisilazane (H(hmds)) in liquid ammonia. Recrystallization of solvent-free alkali metal hexamethyldisilazanides [A(hmds)]n of sodium to cesium from solutions containing 2,2,5,5-tetramethyltetrahydrofuran (Me4THF, thf*) yields the dinuclear complexes [(thf*)A(hmds)]2, which show a rather asymmetric coordination behavior of the bulky ether ligand with strongly bent A-A-O moieties for the heavier K, Rb, and Cs congeners, whereas in the Na complex, the ether ligand is clamped between the trimethylsilyl groups. In hydrocarbon solutions, dissociation of these compounds is observed leading to the liberation of this bulky and weakly binding cyclic ether.

DOI 10.1039/c8dt01539b
ISSN 1477-9234
Citation Dalton Trans. 2018;47(36):1256212569.

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