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

The protonolysis reaction of heterobimetallic peralkylated complexes [Ln(AIR 4 ) 2 ] n (Ln = Sm, Yb; R = Me, Et) with 2 equiv of HOC 6 H 2 tBu 2 -2,6-Me-4 affords the bis(trialkylaluminum) adducts Ln[(μ-OAr tBu,Me )(μ-R)A1R 2 ] 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[(μ-OAr iPr,H ) 2 AlR 2 ] 2 (Ln = Yb, R = Me; Ln = Sm, R = Et), Yb[(u-OAr iPr,H )(μ-Et)AlEt 2 ] 2 (THF), and [Et 2 Al(μ-OAr iP,H ) 2 Yb(μ-Et) 2 AlEt 2 ] 2 . The solid-state structures of serendipitous alumoxane complex Sm[(μ-OAr tBu,Me )AlEt 2 OAlEt 2 (μ-OAr tBu,Me )](toluene) and dimeric AlMe 3 -adduct complex [(AlMe 3 )(μ-OAr tBu,Me )Sm(μ-OAr tBu,Me ) 2 Sm(μ-OAr tBu,Me )(AlMe 3 )] were also determined by X-ray crystallography. While the former can be discussed as a typical hydrolysis product of Sm[(μ-OAr tBu,Me )(μ-Et)AlEt 2 ] 2 , the latter was isolated from the 1:1 reaction of [Sm(AlEt 4 ) 2 ] n with HOAr tBu,Me .