Calcium and Magnesium Bis(β-diketiminate) Complexes: Impact of the Alkylene Bridge on Schlenk-Type Rearrangements.

Dinuclear heteroleptic alkaline-earth-metal complexes are interesting synthetic targets because the close proximity of two metals allows for cooperative effects. However, these complexes are also prone to undergoing Schlenk-type rearrangements, affording less-active homoleptic complexes. Here we present the metalation of bis(β-diketimine) ligands possessing flexible bridging groups, i.e., 1,2-ethylene, 1,3-propylene, and trans-1,2-cyclohexylene, using calcium and magnesium precursors. Four mononuclear homoleptic calcium complexes were obtained, highlighting the pronounced tendency of calcium to undergo Schlenk-like redistributions. In the case of magnesium, however, the bridging group plays a crucial role, yielding seven dinuclear heteroleptic complexes but also one mononuclear and one dinuclear homoleptic complexes. In addition, a trinuclear mixed heteroleptic-homoleptic magnesium complex, which is a rare example of an intermediate of the Schlenk equilibrium, was isolated.