Journal
INORGANICA CHIMICA ACTA
Volume 374, Issue 1, Pages 429-434Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ica.2011.03.030
Keywords
Calcium; Amides; Hauser bases; Metathesis reactions; Schlenk equilibrium; Superbases
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Funding
- German Research Foundation (DFG)
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The metathetical reaction of calcium diiodide with KNR2 in the presence of N,N,N',N'-tetramethylethylendiamine yields the corresponding amido calcium bases [(tmeda)Ca(tmp)(2)] (1), [(tmeda)Ca{N(SiMe3)(2)}(2)] (3), and [(tmeda)Ca(NiPr2)(2)] (4) regardless of the stoichiometric ratio of the starting compounds. All compounds are highly air and moisture sensitive. Only in the case of NR2 being a tmp group very few crystals of the Hauser base-type dimeric derivative [(tmeda)Ca(tmp)(mu-I)](2) (2) with bridging iodide ions can be isolated. In all these calcium complexes the amides are bound terminally and contain planarily coordinated nitrogen atoms. The calcium complex [(tmeda)Ca(NiPr2)(2)] (4) is much more reactive than the lighter magnesium congener and therefore, it has to be stored below 0 degrees C in order to avoid decomposition reactions. (C) 2011 Elsevier B. V. All rights reserved.
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