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.show moreshow less

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Metadaten
Author: Anna Hanft, Dennis Rottschäfer, Nele Wieprecht, Felix Geist, Krzysztof Radacki, Crispin LichtenbergORCiD
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):License LogoCC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International