Heteroleptic Heavier Alkaline Earth Metal Amide Complexes Stabilized by a Superbulky β‑Diketiminate Ligand

Heteroleptic alkaline earth metal (Ae = Ca, Sr, Ba) amide complexes with the superbulky β-diketiminate ligand ^DIPePBDI (CH­[C­(Me)­N-DIPeP]₂, DIPeP = 2,6-di-iso-pentylphenyl) have been prepared by direct deprotonation of ^DIPePBDI-H with either AeN′′₂ or AeN′′₂·(THF)₂ (N′′ = N­(SiMe₃)₂). Despite long reaction times of 5–14 days, this convenient one-step synthetic method has the major advantage that metal-pure products are obtained in generally quantitative yields. All (^DIPePBDI)­AeN′′ and (^DIPePBDI)­AeN′′·THF complexes are monomeric and stabilized by agostic metal···Me₃Si and metal···iso-pentyl interactions. They are highly soluble in toluene and indefinitely stable toward ligand scrambling, even after 2 weeks at 140 °C. The same series with the smaller ^DIPPBDI ligand (CH­[C­(Me)­N-DIPP]₂, DIPP = 2,6-di-iso-propylphenyl) could, except for Ca, also be prepared by direct ligand deprotonation. The (^DIPPBDI)­CaN′′ and (^DIPPBDI)­CaN′′·THF complexes are stable toward ligand exchange up to 110 °C. Whereas THF-free (^DIPPBDI)­SrN′′ and (^DIPPBDI)­BaN′′ decompose at 50 and 20 °C, respectively, their THF adducts were found to be stable up to 60 °C. This is, however, strongly dependent on complex purity. Slight hydrolysis or contamination with KN′′ accelerates ligand scrambling. Therefore, partial hydrolysis and salt metathesis routes that involve KN′′ should be avoided when synthesizing heteroleptic complexes of the heavier Ae metals.