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Synthesis, structure, and stereochemical non-rigidity of bis[(2,2-dimethyl-4-oxo-2H-benzo[e][1,3]oxazin-3(4H)-yl)methyl] dichlorosilane and -germane

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Abstract

Bis[(2,2-dimethyl-4-oxo-2H-benzo[e][1,3]oxazin-3(4H)-yl)methyl]dichlorosilane (1) and -germane (2) were synthesized by the reaction of 2,2-dimethyl-3-(trimethylsilyl)-2H-benzo[e][1,3]oxazin-3(4H)-one with bis(chloromethyl)dichlorosilane and -germane, respectively, taken in a ratio of 2 : 1. The structures of these compounds were determined and their stereodynamic behavior in solution was studied by multinuclear (1H, 13C, and 29Si) and twodimensional (1H, 13C COSY, HETCOR) NMR spectroscopy. The 29Si NMR spectroscopic study of a solution of complex 1 provides evidence that the silicon atom in this complex is pentacoordinate. The X-ray diffraction study showed that the germanium atom in complex 2 in the solid state is hexacoordinate. The permutation isomerization in the coordination units of complexes 1 and 2 was found and investigated by dynamic 1H NMR spectroscopy. Different mechanisms of stereodynamic transformations are suggested and discussed.

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Authors and Affiliations

  1. N. I. Pirogov Russian National Research Medical University, 1 ul. Ostrovityanova, 117997, Moscow, Russian Federation

    Vad. V. Negrebetsky, E. P. Kramarova, D. E. Arkhipov, A. A. Korlyukov, A. G. Shipov & Yu. I. Baukov

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991, Moscow, Russian Federation

    D. E. Arkhipov & A. A. Korlyukov

Authors
  1. Vad. V. Negrebetsky
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  2. E. P. Kramarova
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  3. D. E. Arkhipov
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  4. A. A. Korlyukov
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  5. A. G. Shipov
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  6. Yu. I. Baukov
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Corresponding authors

Correspondence to Vad. V. Negrebetsky or A. A. Korlyukov.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1808—1813, August, 2015.

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Negrebetsky, V.V., Kramarova, E.P., Arkhipov, D.E. et al. Synthesis, structure, and stereochemical non-rigidity of bis[(2,2-dimethyl-4-oxo-2H-benzo[e][1,3]oxazin-3(4H)-yl)methyl] dichlorosilane and -germane. Russ Chem Bull 64, 1808–1813 (2015). https://doi.org/10.1007/s11172-015-1075-3

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