Assessing Alkali-Metal Effects in the Structures and Reactivity of Mixed-Ligand Alkyl/Alkoxide Alkali-Metal Magnesiates.

Abstract

Advancing the understanding of using alkali‐metal alkoxides as additives to organomagnesium reagents in Mg−Br exchange reactions, a homologous series of mixed‐ligand alkyl/alkoxide alkali‐metal magnesiates [MMg(CH2SiMe3)2(dmem)]2 [dmem=2‐{[2‐(dimethylamino)ethyl]methylamino} ethoxide; M=Li, 1; Na, 2; (THF)K, 3] has been prepared. Structural and spectroscopic studies have established the constitutions of these heteroleptic/heterometallic species, which are retained in arene solution. Evaluation of their reactivity towards 2‐bromoanisole has uncovered a marked alkali‐metal effect with potassium magnesiate 3 being the most efficient of the three ate reagents. Studies probing the constitution of the exchange product from this reaction suggest that the putative [KMgAr2(dmem)]2 (Ar=o‐OMe−C6H4) intermediate undergoes redistribution into its single metal components [KAr]n and [MgAr(dmem)]2 (5). This process can be circumvented by using a different potassium alkoxide containing an aliphatic chain such as KOR’ (R’=2‐ethylhexyl) which undergoes co‐complexation with Mg(CH2SiMe3) to give [KMg(CH2SiMe3)2(OR’)]2 (7). This ate, in turn, reacts quantitatively with 2‐bromoanisole furnishing [KMgAr2(OR’)]2 (9) which is stable in solution as a bimetallic compound. Collectively this work highlights the complexity of these alkali‐metal mediated Mg−Br exchange reactions, where each reaction component can have a profound effect not only on the success of the reaction; but also the stability of the final metalated intermediates prior to their electrophilic interception.