Abstract
We present complexes of alkali metal ions and the ammonium ion with the large cyclodimethylsiloxanes D7 and D8 (D = Me2SiO). The formation of such complexes is accompanied by rearrangements of the ligands to form complexes with a suitable ring size for the metal used. These rearrangements could be suppressed by suitable reaction conditions and rapid work‐up of the reaction mixtures. This enabled the isolation of [Li(D7)][GaI4] (1), [Li(D8)][GaI4] (2), [Na(D8)][GaI4] (3), [K(D8)][GaI4] (4) and [NH4(D8)][GaI4] (5). All of the prepared compounds were analysed using single‐crystal X‐ray diffraction as well as multinuclear NMR spectroscopy. This reveals very different coordination modes in the compounds obtained.
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