Synthese von substituierten Calcium-bis(disilylamiden) mittels der Transmetallierung von Zinn(II)- und Zinn(IV)-amiden |
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Authors: | Matthias Westerhausen Jrg Greul Hans-Dieter Hausen Wolfgang Schwarz |
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Institution: | Matthias Westerhausen,Jörg Greul,Hans-Dieter Hausen,Wolfgang Schwarz |
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Abstract: | Synthesis of Substituted Calcium-bis(disilylamides) by Transmetalation of Tin(II) and Tin(IV) Amides Stannylenes as well as stannanes with substituted disilylamino groups are valuable synthons for the synthesis of alkaline earth metal bis(disilylamides) via the transmetallation reaction. Whereas bis2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentyl]stannylene 1 is a suitable reagent for this type of reaction, bistrimethylsilyl-tris(trimethylsilyl)silylamino]stannylene 2 (monoclinic, P21/c, a = 1492.6(2), b = 1705.2(2), c = 1865.3(3) pm, β = 109.03(2)º, Z = 4) is not only attacked at the Sn? N-bond but also the N? Si-bond is cleaved by calcium metal. Similar light sensitivity as for 2 is observed for the mercury bistrimethylsilyl-tris(trimethylsilyl)silylamide] 3 , the homolytic M? N-bond cleavage leads to the formation of the trimethylsilyl-tris(trimethylsilyl)silylamino radical (g = 2.00485; a(N) = 16.2 G). The calcium tin exchange reaction of 1 in THF yields tris(tetrahydrofuran-O)calcium-bis2,2,5,5-tetramethyl-2,5-disilaaza-cyclo-pentanide] 4 (monoclinic, P21/n, a = 1060.9(2), b = 1919.3(5), c = 1686.0(3) pm, β = 90.30(2)º, Z = 4). The stannanes Men-4SnN(SiMe3)2]n with n = 1 or 2 are also valuable materials for the synthesis of bis(tetrahydrofuran-O)calcium-bisbis(trimethylsilyl)amide]. |
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Keywords: | Transmetalation Calcium Stannylene Tin Amide NMR Spectroscopy X-Ray Structure |
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