Distinct Reaction Pathways of Peralkylated Ln super(II)Al super(III) Heterobimetallic Complexes with Substituted Phenols

• Published in: Inorganic chemistry 2008-06, Vol.47 (11), p.4696-4705
• Main Authors: Sommerfeldt, Hanne-Marthe, Meermann, Christian, Tornroos, Karl W, Anwander, Reiner
• Format: Article
• Language: English
• Subjects: Adducts; Crystallography; Formations; Hydrolysis; Ligands; Pathways; Phenols; X-rays
• ISSN: 0020-1669
• DOI: 10.1021/ic702517s

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