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Soft Interactions with Hard Lewis acids: Generation of Mono- and Dicationic Alkaline-Earth Metal Arene-Complexes by Direct Oxidation.

Abstract

Abstract: The synthesis of the first unsupported dicationic arene complexes of Calcium and Strontium [(η6-HMB)­AE(oDFB)4]2+ is reported (HMB = hexamethylbenzene; AE = Alkaline Earth metal; oDFB = ortho-difluoro­benzene). They were prepared by direct oxidation of the elemental metals em­ploying the ligand-forming radical cation salt [HMB][WCA] as oxidant (WCA = [Al(ORF)4] or [µF-{Al(ORF)3}2]; RF = C(CF3)3). In addition, monocationic η6-HMB complexes of Calcium, Strontium and Barium supported by coordination of the monodentate anion [F-Al(ORF)3] are reported. In all examples, almost un­distor­ted η6-HMB coordination is observed with rather short M-arenecentroid distances approaching those else observed with the isoelectronic, but negatively charged pentamethylcyclopentadienyl ligand. The structure and bonding, thermodynamic stability and Lewis acidity (Fluoride / Hydride Ion Affinities FIA / HIA) of the generated complexes was assessed by DFT methods. It followed that the gaseous dications [(η6-HMB)­AE(oDFB)4]2+  are extreme hard Lewis acids that retain FIAs close to superacidity in solution.

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Article information


Submitted
10 Dec 2019
Accepted
12 Jan 2020
First published
13 Jan 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Accepted Manuscript
Article type
Edge Article

Soft Interactions with Hard Lewis acids: Generation of Mono- and Dicationic Alkaline-Earth Metal Arene-Complexes by Direct Oxidation.

M. Schorpp and I. Krossing, Chem. Sci., 2020, Accepted Manuscript , DOI: 10.1039/C9SC06254H

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