Isolation of a diylide-stabilized stannylene and germylene
- The preparation of the first stable diylide-substituted stannylene and germylene ( \(\bf{Y_{2}E}\), with E=Ge, Sn and Y=PPh\(_{3}\)-C-SO\(_{2}\)Tol]\(^{−}\)) is reported. The synthesis is easily accomplished in one step from the sulfonyl-substituted metalated ylide \(\bf{YNa}\) and the corresponding ECl\(_{2}\) precursors. \(\bf{Y_{2}Ge}\) and \(\bf{Y_{2}Sn}\) exhibit unusual structures in the solid state and in solution, in which the three adjacent lone pairs in the C-E-C linkage are arranged coplanar to each other. As shown by DFT studies, this bonding situation is preferred over the typical π-donation from the ligands into the empty p-orbital at the metal due to the strong anion-stabilizing ability of the sulfonyl groups in the ylide backbone and their additional coordination to the metal. The alignment of the three lone pairs leads to a remarkable boost of the HOMO energy and thus of the donor strengths of the tetrylenes. Hence, \(\bf{Y_{2}Ge}\) and \(\bf{Y_{2}Sn}\) become stronger donors than their diamino or diaryl congeners and comparable to cyclic alkyl(amino)carbenes. First reactivity studies confirm the high reactivity of \(\bf{Y_{2}Ge}\) and \(\bf{Y_{2}Sn}\), which for example undergo an intramolecular C−H activation reaction via metal–ligand cooperation.
Author: | Viktoria H. Däschlein-GessnerORCiDGND, Chandrajeet MohapatraORCiDGND, Lennart T. ScharfGND, Thorsten ScherpfGND, Bert MallickGND, Kai-Stephan FeichtnerGND, Christopher M. SchwarzGND |
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URN: | urn:nbn:de:hbz:294-89189 |
DOI: | https://doi.org/10.1002/anie.201902831 |
Parent Title (English): | Angewandte Chemie International Edition |
Subtitle (English): | enhanced donor strength through coplanar lone pair alignment |
Publisher: | Wiley |
Place of publication: | Hoboken, New Jersey |
Document Type: | Article |
Language: | English |
Date of Publication (online): | 2022/05/09 |
Date of first Publication: | 2019/03/22 |
Publishing Institution: | Ruhr-Universität Bochum, Universitätsbibliothek |
Tag: | germylenes; main group elements; stannylenes; subvalent compounds; ylides |
Volume: | 58 |
Issue: | 22 |
First Page: | 7459 |
Last Page: | 7463 |
Institutes/Facilities: | Lehrstuhl für Anorganische Chemie II |
Dewey Decimal Classification: | Naturwissenschaften und Mathematik / Chemie, Kristallographie, Mineralogie |
faculties: | Fakultät für Chemie und Biochemie |
Licence (English): | Creative Commons - CC BY-NC-ND 4.0 - Attribution-NonCommercial-NoDerivatives 4.0 International |