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 HOC6H2 tBu2-2,6-Me-4 affords the bis(trialkylaluminum) adducts Ln[(μ-OAr tBu,Me)(μ-R)AlR2]2 in good yields. Analogous reactions with the less sterically demanding iPr-substitu...

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Published in:Inorganic chemistry 2008-06, Vol.47 (11), p.4696-4705
Main Authors: Sommerfeldt, Hanne-Marthe, Meermann, Christian, Törnroos, Karl W, Anwander, Reiner
Format: Article
Language:English
Online Access:Get full text
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Summary:The protonolysis reaction of heterobimetallic peralkylated complexes [Ln(AlR4)2] n (Ln = Sm, Yb; R = Me, Et) with 2 equiv of HOC6H2 tBu2-2,6-Me-4 affords the bis(trialkylaluminum) adducts Ln[(μ-OAr tBu,Me)(μ-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[(μ-OAr iPr,H)2AlR2]2 (Ln = Yb, R = Me; Ln = Sm, R = Et), Yb[(μ-OAr iPr,H)(μ-Et)AlEt2]2(THF), and [Et2Al(μ-OAr iPr,H)2Yb(μ-Et)2AlEt2]2. The solid-state structures of serendipitous alumoxane complex Sm[(μ-OAr tBu,Me)AlEt2OAlEt2(μ-OAr tBu,Me)](toluene) and dimeric AlMe3-adduct complex [(AlMe3)(μ-OAr tBu,Me)Sm(μ-OAr tBu,Me)2Sm(μ-OAr tBu,Me)(AlMe3)] 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)AlEt2]2, the latter was isolated from the 1:1 reaction of [Sm(AlEt4)2]n with HOAr tBu,Me.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic702517s