Electronic modification of a sterically demanding anionic pyridine ligand
Abstract: The sterically demanding anionic pyridine ligand [4-(Ph3B)-2,6-Mes2py]− ([1]−) was used in salt metathesis reactions in order to obtain main group and transition metal complexes. Instead, reduction reactions were observed and identified as single electron transfer processes from [1]− to the respective Lewis acidic cations. The electron transfer was confirmed by reduction of the trityl cation. In order to reduce the reductive power of [1]− the borate function of the ligand was substituted with strongly electron withdrawing 3,5-bis(trifluoromethyl)phenyl groups to give [1F]−. The redox potential was shifted from +0.56 V to +1.32 V and hence, [1F]− cannot reduce the trityl cation in contrast to [1]−. Consequently, the measured pKa value of 1F-H (16.44) was lowered by two pKa units compared with 1-H. Unfortunately, [1F]− still undergoes single electron transfer processes when used in salt metathesis reactions. We synthesized the anionic borane adduct [Li(THF)4][1F-BH3] which demonstrates that [1F]− can be used as a ligand in main group chemistry. The determination of the crystal structures of [Li(THF)4][1F] and [Li(THF)4][1F-BH3] revealed separated ion pairs while their analogs with the more electron rich [1]− are contact ion pairs
- Location
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Deutsche Nationalbibliothek Frankfurt am Main
- Extent
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Online-Ressource
- Language
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Englisch
- Notes
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Zeitschrift für anorganische und allgemeine Chemie. - 648, 19 (2022) , e202200136, ISSN: 1521-3749
- Classification
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Chemie
- Event
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Veröffentlichung
- (where)
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Freiburg
- (who)
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Universität
- (when)
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2022
- Creator
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Schmidlin, Nadja Maria Clara
Radtke, Valentin
Schmidt, Alexei
Lõkov, Märt
Leito, Ivo
Böttcher, Tobias
- DOI
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10.1002/zaac.202200136
- URN
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urn:nbn:de:bsz:25-freidok-2302728
- Rights
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Last update
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25.03.2025, 1:50 PM CET
Data provider
Deutsche Nationalbibliothek. If you have any questions about the object, please contact the data provider.
Associated
- Schmidlin, Nadja Maria Clara
- Radtke, Valentin
- Schmidt, Alexei
- Lõkov, Märt
- Leito, Ivo
- Böttcher, Tobias
- Universität
Time of origin
- 2022
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