Aminotroponiminates: Impact of the NO\(_{2}\) Functional Group on Coordination, Isomerisation, and Backbone Substitution
Please always quote using this URN: urn:nbn:de:bvb:20-opus-256988
- Aminotroponiminate (ATI) ligands are a versatile class of redox-active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron-withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro-substituent in the backbone. It is demonstratedAminotroponiminate (ATI) ligands are a versatile class of redox-active and potentially cooperative ligands with a rich coordination chemistry that have consequently found a wide range of applications in synthesis and catalysis. While backbone substitution of these ligands has been investigated in some detail, the impact of electron-withdrawing groups on the coordination chemistry and reactivity of ATIs has been little investigated. We report here Li, Na, and K salts of an ATI ligand with a nitro-substituent in the backbone. It is demonstrated that the NO2 group actively contributes to the coordination chemistry of these complexes, effectively competing with the N,N-binding pocket as a coordination site. This results in an unprecedented E/Z isomerisation of an ATI imino group and culminates in the isolation of the first “naked” (i. e., without directional bonding to a metal atom) ATI anion. Reactions of sodium ATIs with silver(I) and tritylium salts gave the first N,N-coordinated silver ATI complexes and unprecedented backbone substitution reactions. Analytical techniques applied in this work include multinuclear (VT-)NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations.…
Author: | Anna Hanft, Dennis Rottschäfer, Nele Wieprecht, Felix Geist, Krzysztof Radacki, Crispin LichtenbergORCiD |
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URN: | urn:nbn:de:bvb:20-opus-256988 |
Document Type: | Journal article |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Anorganische Chemie |
Language: | English |
Parent Title (English): | Chemistry—A European Journal |
Year of Completion: | 2021 |
Volume: | 27 |
Issue: | 57 |
Pagenumber: | 14250–14262 |
Source: | Chemistry—A European Journal 2021, 27(57):14250–14262. DOI: 10.1002/chem.202102324 |
DOI: | https://doi.org/10.1002/chem.202102324 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 546 Anorganische Chemie |
Tag: | alkali metal; aminotroponiminates; electrophilic substitution; isomerisation; non-coordinate anionic ligand |
Release Date: | 2022/03/08 |
Licence (German): | CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International |