Issue 36, 2018

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

Abstract

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.

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

Supplementary files

Article information

Article type
Paper
Submitted
18 4月 2018
Accepted
18 5月 2018
First published
18 5月 2018

Dalton Trans., 2018,47, 12562-12569

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

S. Krieck, P. Schüler, H. Görls and M. Westerhausen, Dalton Trans., 2018, 47, 12562 DOI: 10.1039/C8DT01539B

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