The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond

Hartmann D, Thorwart T, Muller R, Thusek J, Schwabedissen J, Mix A, Lamm J-H, Neumann B, Mitzel NW, Greb L (2021)
Journal of the American Chemical Society.

Zeitschriftenaufsatz | E-Veröff. vor dem Druck | Englisch
 
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Autor*in
Hartmann, Deborah; Thorwart, Thaddaus; Muller, Rosa; Thusek, Jean; Schwabedissen, JanUniBi; Mix, AndreasUniBi; Lamm, Jan-HendrikUniBi; Neumann, BeateUniBi; Mitzel, Norbert W.UniBi; Greb, Lutz
Abstract / Bemerkung
Catechols occupy a unique role in the structural, bio-, and geochemistry of silicon. Although a wealth of knowledge exists on their hypercoordinate complexes, the structure of tetracoordinate bis(catecholato)silane, Si(catH)2 1, has been enigmatic since its first report in 1951. Indeed, the claim of a planar-tetracoordinated silicon in 1 triggered a prominent debate, which is unsettled to this day. Herewith, we present a comprehensive structural study on 1 and derivatives in the gas phase by electron diffraction, in a neon matrix by IR spectroscopy, in solution by diffusion NMR spectroscopy, and in the solid-state by X-ray diffraction and MAS NMR spectroscopy, complemented by high-level quantum-chemical computations. The compound exhibits unprecedented phase adaptation. In the gas phase, the monomeric bis(catecholato)silane is tetrahedral, but in the condensed phase, it is metastable toward oligomerization up to a degree controllable by the type of catechol, temperature, and concentration. For the first time, spectroscopic evidence is obtained for a rapid Si-O sigma-bond metathesis reaction. Hence, this study sorts out a long-lasting debate and confirms dynamic covalent features for our Earth's crust's most abundant chemical bond.
Erscheinungsjahr
2021
Zeitschriftentitel
Journal of the American Chemical Society
eISSN
1520-5126
Page URI
https://pub.uni-bielefeld.de/record/2958721

Zitieren

Hartmann D, Thorwart T, Muller R, et al. The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond. Journal of the American Chemical Society. 2021.
Hartmann, D., Thorwart, T., Muller, R., Thusek, J., Schwabedissen, J., Mix, A., Lamm, J. - H., et al. (2021). The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond. Journal of the American Chemical Society. https://doi.org/10.1021/jacs.1c09746
Hartmann, D., Thorwart, T., Muller, R., Thusek, J., Schwabedissen, J., Mix, A., Lamm, J. - H., Neumann, B., Mitzel, N. W., and Greb, L. (2021). The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond. Journal of the American Chemical Society.
Hartmann, D., et al., 2021. The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond. Journal of the American Chemical Society.
D. Hartmann, et al., “The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond”, Journal of the American Chemical Society, 2021.
Hartmann, D., Thorwart, T., Muller, R., Thusek, J., Schwabedissen, J., Mix, A., Lamm, J.-H., Neumann, B., Mitzel, N.W., Greb, L.: The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond. Journal of the American Chemical Society. (2021).
Hartmann, Deborah, Thorwart, Thaddaus, Muller, Rosa, Thusek, Jean, Schwabedissen, Jan, Mix, Andreas, Lamm, Jan-Hendrik, Neumann, Beate, Mitzel, Norbert W., and Greb, Lutz. “The Structure of Bis(catecholato)silanes: Phase Adaptation by Dynamic Covalent Chemistry of the Si-O Bond”. Journal of the American Chemical Society (2021).

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