New organogermanium cations [RGe(OCH2CH2NME2)2]+ with intramolecular N→Ge coordination bonds |
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Authors: | I. A. Portnyagin V. V. Lunin M. S. Nechaev |
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Affiliation: | (1) Department of Chemistry, M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119992 Moscow, Russian Federation |
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Abstract: | New organohalogermanes RGe(OCH2CH2NMe2)2X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N→Ge coordination bond were synthesized. According to the 1H and 13C NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The structures and relative stabilities of different isomers of compounds 4–7 were studied by quantum chemical calculations at the density functional level of theory. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 892–900, May, 2007. |
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Keywords: | organogermanium compounds hypercoordinated compounds germyl cations intramolecular coordination bonds 1H and 13C NMR spectroscopy density functional method |
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