Inorganic Chemistry, Vol.47, No.11, 4696-4705, 2008
Distinct reaction pathways of peralkylated Ln(II)Al(III) heterobimetallic complexes with substituted phenols
The protonolysis reaction of heterobimetallic peraikylated cor plexes [Ln(AlR4)(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[(mu-OArtBu,Me) (mu-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[(mu-OAriPr,H)(2)AlR2](2) (Ln = Yb, R = Me; Ln = Sm, R = Et), Yb[(mu-OAriPr,H) (mu-Et)AlEt2](2)(THF), and [Et2Al(mu-OAriPr,H)(2)Yb(mu-Et)(2)AlEt2](2). The solid-state structures of serendipitous alumoxane complex Sm[(mu-OArtBu,Me)AlEt2OAlEt2(mu-OArtBu,Me)](toluene) and dimeric AlMeFadduct complex [(AlMe3)(mu-OArtBu,Me) Sm(mu-OArtBu,Me)(2)Sm(mu-OArtBu,Me)(AlMe3)] were also determined by X-ray crystallography. While the former can be discussed as a typical hydrolysis product of Sm[(mu-OArtBu,Me) (mu-Et)AlEt2](2), the latter was isolated from the 1:1 reaction of [Sm(AlEt4)(2)], with HOArtBu,Me.