Stabilization of Potent Co(II)-based Lewis Acids with Weakly Basic Ligands.

Autor: Jadwiszczak MJ; Centre of New Technologies, University of Warsaw, Banacha 2c, PL-02097, Warsaw, Poland., Malinowski PJ; Centre of New Technologies, University of Warsaw, Banacha 2c, PL-02097, Warsaw, Poland.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2023 Feb 07; Vol. 29 (8), pp. e202202976. Date of Electronic Publication: 2022 Dec 21.
DOI: 10.1002/chem.202202976
Abstrakt: Pairing cations with weakly coordinating anions (WCAs) often renders them highly Lewis-acidic and extremely reactive. Although these features are often desirable, excessive reactivity of a cation may lead to decomposition of solvents or WCAs, hindering isolation, storage and practical use of such species. In an attempt to mitigate the problem, we introduce a series of readily available novel Co(II)-WCA salts with the metal center stabilized by weakly bound ligands: SO 2 , halogenated acetonitriles and nitromethane with comprehensive characterization including structural, magnetic and spectral (IR) properties as well as thermal stability assessment. The use of these simple yet rarely encountered ligands yields mostly stable and highly Lewis-acidic complexes, in some cases comparable to SbF 5 according to calculated Fluoride Ion Affinities. Highly acidic character of the species is also reflected in observed reactivity. Since the most convenient route towards the Co(II) complexes leads through silver salts, the results are complemented with characterization of a series of novel Ag(I) complexes with abovementioned ligands. Experimental part is backed with DFT calculations which gives insight into the structure and energetics of presented Co(II) complexes and shows that Co(II) center is available for substrates like olefins. This makes them good candidates for catalysts in reactions requiring the presence of Lewis acids.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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