The structure of Bis(catecholato)silanes: phase adaptation by dynamic covalent chemistry of the Si-O bond
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...
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| Main Authors: | , , , , , , , , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
October 23, 2021
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| In: |
Journal of the American Chemical Society
Year: 2021, Volume: 143, Issue: 44, Pages: 18784-18793 |
| ISSN: | 1520-5126 |
| DOI: | 10.1021/jacs.1c09746 |
| Online Access: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/jacs.1c09746
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| Author Notes: | Deborah Hartmann, Thaddäus Thorwart, Rosa Müller, Jean Thusek, Jan Schwabedissen, Andreas Mix, Jan-Hendrik Lamm, Beate Neumann, Norbert W. Mitzel, and Lutz Greb |
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| 245 | 1 | 4 | |a The structure of Bis(catecholato)silanes |b phase adaptation by dynamic covalent chemistry of the Si-O bond |c Deborah Hartmann, Thaddäus Thorwart, Rosa Müller, Jean Thusek, Jan Schwabedissen, Andreas Mix, Jan-Hendrik Lamm, Beate Neumann, Norbert W. Mitzel, and Lutz Greb |
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| 520 | |a 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 σ-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. | ||
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