Distinct reaction pathways of peralkylated LnIIAlIII heterobimetallic complexes with substituted phenols.

The protonolysis reaction of heterobimetallic peralkylated complexes [Ln(AlR4)2]n (Ln=Sm, Yb; R=Me, Et) with 2 equiv of HOC 6H 2 tBu 2-2,6-Me-4 affords the bis(trialkylaluminum) adducts Ln[(micro-OArtBu,Me)(micro-R)AlR2]2 in good yields. Analogous reactions with the less sterically demanding iPr-substituted phenol result in ligand redistributions and formation of X-ray structurally evidenced Ln[(micro-OAriPr,H) 2AlR2]2 (Ln=Yb, R=Me; Ln=Sm, R=Et), Yb[(micro-OAriPr,H)(micro-Et)AlEt2]2(THF), and [Et2Al(micro-OAriPr,H) 2Yb(micro-Et)2AlEt2]2. The solid-state structures of serendipitous alumoxane complex Sm[(micro-OArtBu,Me)AlEt2OAlEt2(micro-OArtBu,Me)](toluene) and dimeric AlMe 3-adduct complex [(AlMe3)(micro-OArtBu,Me)Sm(micro-OArtBu,Me) 2Sm(micro-OArtBu,Me)(AlMe3)] were also determined by X-ray crystallography. While the former can be discussed as a typical hydrolysis product of Sm[(micro-OArtBu,Me)(micro-Et)AlEt2]2, the latter was isolated from the 1:1 reaction of [Sm(AlEt4)2]n with HOArtBu,Me.