Abstract
Recently, we have witnessed significant progress with regard to the synthesis of molecular alkaline earth metal reagents and catalysts. To provide new precursors for light alkaline earth metal chemistry, molecular aryloxide and alkoxide complexes of beryllium and magnesium are reported. The reaction of beryllium chloride dietherate with two equivalents of 1,3-diisopropyl-4,5-dimethylimidizol-2-ylidine (sIPr) results in the formation of a bis(N-heterocyclic carbene) (NHC) beryllium dichloride complex, (sIPr)2BeCl2 (1). Compound 1 reacts with lithium diisopropylphenoxide (LiODipp) or sodium ethoxide (NaOEt) to form the terminal aryloxide (sIPr)Be(ODipp)2 (2) and alkoxide dimer [(sIPr)Be(OEt)Cl]2 (3), respectively. Compounds 2 and 3 represent the first beryllium alkoxide and aryloxide species supported by NHCs. Structurally related dimers of magnesium, [(sIPr)Mg(OEt)Brl]2 (4) and [(sIPr)Mg(OEt)Me]2 (5), were also prepared. Compounds 1-5 were characterized by single crystal X-ray diffraction studies, 1H, 13C, and 9Be NMR spectroscopy where applicable.
Highlights
The chemistry of alkaline earth metal oxides has historically been associated with materials of high thermal stability and poor solubility [1]
The utilization of neutral carbenes in Ae metal chemistry has attracted a significant amount of attention, which has resulted in a substantial amount of new chemistry [36,37]. Might these ligands play a role in the formation of Ae oxides? far, only two examples of NHC–magnesium alkoxideor aryloxide-containing complexes have been crystallographically characterized [38,39]
Synthesis of a complex containing two untethered NHCs bound to a mononuclear beryllium halide
Summary
The chemistry of alkaline earth metal oxides has historically been associated with materials of high thermal stability and poor solubility [1]. Chemists routinely employ synthetic strategies to decorate Ae-O bonds with various aryl or alkyl functionalities and/or bulky ligands to impart both stability and solubility. Even under these strict conditions, Ae-O moieties have a propensity to form insoluble polymeric structures, after loss of stabilizing ligands [3,4]. The utilization of neutral carbenes in Ae metal chemistry has attracted a significant amount of attention, which has resulted in a substantial amount of new chemistry [36,37] Might these ligands play a role in the formation of Ae oxides? Of which a number of examples are known [47,48]
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