An η3‐Bound Allyl Ligand on Magnesium in a Mechanochemically Generated Mg/K Allyl Complex

Milling two equivalents of K1,3‐(SiMe₃)₂C₃H₃] (=KA′]) with MgX₂ (X=Cl, Br) produces the allyl complex K₂MgA′₄] ( 1 ). Crystals grown from toluene are of the solvated species ((η⁶‐tol)K)₂MgA′₄] ( 1 ?2(tol)]), a trimetallic monomer with both bridging and terminal (η¹) allyl ligands. When recrystallized from hexanes, the unsolvated 1 forms a 2D coordination polymer, in which the Mg is surrounded by three allyl ligands. The C?C bond lengths differ by only 0.028 Å, indicating virtually complete electron delocalization. This is an unprecedented coordination mode for an allyl ligand bound to Mg. DFT calculations indicate that in isolation, an η³‐allyl configuration on Mg is energetically preferred over the η¹‐ (σ‐bonded) arrangement, but the Mg must be in a low coordination environment for it to be experimentally realized. Methyl methacrylate is effectively polymerized by 1 , with activities that are comparable to KA′] and greater than the homometallic magnesium complex {MgA′₂}₂].