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Stable Germylenes Derived from 1,2-Bis(arylimino)acenaphthenes

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journal contribution
posted on 2004-07-19, 00:00 authored by Igor L. Fedushkin, Alexandra A. Skatova, Valentina A. Chudakova, Natalie M. Khvoinova, Andrey Yu. Baurin, Sebastian Dechert, Markus Hummert, Herbert Schumann
Metal exchange reactions of the magnesium complexes (dpp-BIAN)Mg(THF)n, (dtb-BIAN)Mg(THF)n, and (bph-BIAN)Mg(THF)n with GeCl2(dioxane) afford the stable germylenes (dpp-BIAN)Ge (1), (dtb-BIAN)Ge(Et2O) (2), and (bph-BIAN)Ge (3), respectively (dpp-BIAN = 1,2-[(2,6-iPr2C6H3)N]2C12H6, dtb-BIAN = 1,2-[(2,5-tBu2C6H3)N]2C12H6, bph-BIAN = 1,2-[(2-PhC6H4)N]2C12H6). Compound 1 is also obtained from (dpp-BIAN)Na4 and GeCl4 in Et2O. The germylenes 13 were characterized by elemental analyses, 1H NMR, 13C NMR, and IR spectroscopy, and X-ray crystal structure analyses. In the monomeric molecules the two imino nitrogen atoms coordinate the germanium atom. The aryl(N) groups are arranged rather orthogonal to the acenaphthenediimine plane. Compound 3 shows an anti geometry with the ortho phenyl substituents of both N-phenyl rings positioned on opposite sides of the acenaphthenediimine plane. The bite angles N−Ge−N are 85.2° (1) and 85.0° (3), respectively. The Ge−N bond distances in 13 range from 1.878 to 1.915 Å.