Endohedral Mixed Aggregates: Sodium Alkoxide Cages with Organic or Inorganic Central Anions and Variable Hull |
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Authors: | Erkam Cebi Dr. Jan Klett |
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Affiliation: | Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10–14, 55128 Mainz, Germany |
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Abstract: | Alkali metal alkoxides are widely used in chemistry due to their Brønsted basic and nucleophilic properties. Potassium alkoxides assist alkyllithium in the metalation of hydrocarbons in Lochmann-Schlosser-bases. Both compounds form mixed aggregates, which enhance the thermal stability, solubility, and the basic reactivity of these mixtures. A very unusual spherical mixed alkoxy aggregate was discovered by Grützmacher et al., where a central dihydrogen phosphide anion is surrounded by a highly dynamic shell of thirteen sodium atoms and a hull of twelve tert-butoxide groups. This structural motif can be reproduced by a reaction of trimethylsilyl compounds of methane, halogens, or pseudo-halogens with excess sodium tert-butoxide. A nucleophilic substitution releases the corresponding anion, which is then encapsulated by the sodium alkoxide units. The compounds are soluble in hydrocarbon solvents, enabling studies of solutions by high-resolution NMR spectroscopy and IR/Raman studies of the crystalline materials. |
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Keywords: | aggregation alkoxide cage compounds isotopic labeling sodium |
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