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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: Hartmann, Deborah (Author) , Thorwart, Thaddäus (Author) , Müller, Rosa (Author) , Thusek, Jean (Author) , Schwabedissen, Jan (Author) , Mix, Andreas (Author) , Lamm, Jan-Hendrik (Author) , Neumann, Beate (Author) , Mitzel, Norbert W. (Author) , Greb, Lutz (Author)
Format: Article (Journal)
Language:English
Published: October 23, 2021
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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Summary: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.
Item Description:Published: October 26, 2021
Gesehen am 05.10.2022
Physical Description:Online Resource
ISSN:1520-5126
DOI:10.1021/jacs.1c09746

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