Recent Developments in Homogeneous Organomagnesium Catalysis

Abstract

Stoichiometric organomagnesium chemistry has continually progressed since its initiation by Victor Grignard over one century ago. Other than acting as a Lewis acid, however, homogeneous magnesium catalysis is a rare topic in the literature. Magnesium catalysts that govern reactions within the coordination sphere of magnesium have only recently begun to appear. This Concept covers recent progress in this young but potentially powerful new chapter of magnesium chemistry.

Magnesium‐Catalyzed Tandem Dehydrogenation‐Dehydrocoupling: An Atom Economical Access to Alkynylboranes

“…In the mechanism, they proved that Mg−H could be involved in the key step, and excluded the formation of the magnesium alkynide. This was consistent with all previous reports of magnesium‐catalyzed hydroboration of imine/aldehydes, ketones, or esters …”

Hydrido Complexes of Calcium: A New Family of Molecular Alkaline‐Earth‐Metal Compounds

“…The coordination numbers for calcium vary from 4to9,while the hydrides exhibit m 2 -tom 6 -bridging bonding modes.Aterminal calcium hydride,w hich is expected to be extremely reactive, remains elusive,b ut may play ar ole in hydrogenation and hydrofunctionalization catalysis.S everal recent discoveries such as n-alkene and benzene alkylation [30] as well as CO [28] and H 2 [40,41] activation will surely boost this research area further. Molecular hydrides of the heavier strontium [37,39,46] and barium [15c,47] have also appeared recently.H omogeneous catalysis by soluble alkaline earth metal compounds is already arapidly growing area, [48] with the hydrido complexes playing ac entral role.…”

Mg(PF6)2-Based Electrolyte Systems: Understanding Electrolyte–Electrode Interactions for the Development of Mg-Ion Batteries

“…In summary, we have for the first time synthesized a Mg(PF 6 ) 2 complex (1), providing access to a group 2 complex containing labile CH 3 CN ligands and weakly coordinating anions that could be used as a general precursor for the formation of alkaline earth metal catalysts or as a reagent itself. 27,28 Furthermore, we have demonstrated successful plating and stripping of Mg from a Mg(PF 6 ) 2 -based electrolyte system. These Mg(PF 6 ) 2 -based electrolytes exhibit a large stability window on Al (>4.0 V vs. Mg) and can be cycled on Mg without resulting in any noticeable loss in electrochemical activity of the Mg electrode over at least 10 cycles.…”