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

Angaben zum Objekt

• Standort: Deutsche Nationalbibliothek Frankfurt am Main
• Umfang: Online-Ressource
• Sprache: Englisch
• Anmerkungen: Zeitschrift für anorganische und allgemeine Chemie. - 648, 19 (2022) , e202200136, ISSN: 1521-3749

Klassifikation und Themen

• Klassifikation: Chemie

Beteiligte, Orts- und Zeitangaben

• Ereignis: Veröffentlichung
• (wo): Freiburg
• (wer): Universität
• (wann): 2022
• Urheber: Schmidlin, Nadja Maria Clara ; Radtke, Valentin ; Schmidt, Alexei ; Lõkov, Märt ; Leito, Ivo ; Böttcher, Tobias

Weitere Informationen

• DOI: 10.1002/zaac.202200136
• URN: urn:nbn:de:bsz:25-freidok-2302728
• Rechteinformation: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
• Letzte Aktualisierung: 15.08.2025, 07:38 MESZ