Synthesis, properties, and x-ray structures of the lanthanide {eta}{sup 6}-arene-bridged aryloxide dimers Ln{sub 2}(O-2,6-i-Pr{sub 2}H{sub 3}){sub 6} and their Lewis base adducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln = Pr, Nd, Sm, Gd, Er, Yb, Lu)
- Los Alamos National Laboratory, NM (United States)
Reaction of 3 equiv of 2,6-diisopropylphenol with Ln[N(SiMe{sub 3}){sub 2}]{sub 3}(Ln=Nd, Sm, Er) in refluxing toluene and subsequent crystallization yield pale blue (Nd), deep yellow (Sm), or light pink (Er) crystals of the tris(aryloxide) complexes Ln{sub 2}(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 6}(Ln = Nd(1), Sm(2), Er(3)) in good yield. X-ray crystallographic studies of 1 and 2 reveal centrosymmetric, dimeric units bridged by {eta}{sup 6}-{pi}-arene interactions of a unique aryloxide ligand. Ln-O bond lengths average 2.122(9) (1,Nd) and 2.101(6) {Angstrom} (2,Sm) for terminal ligands and 2.211(8) (1) and 2.198(5) {Angstrom} (2) for bridging aryloxide ligands. {eta}{sup 6}-Arene bridges hold the dimeric units together with an average Ln-C distance of 3.035 {Angstrom} for 1 and 2.986 and 3.016 {Angstrom} for the two independent molecules in the asymmetric unit of 2. Compounds 1-3 react with THF in toluene solution to give the THF bisadducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln=Nd(4), Sm(5), Er (6)) in essentially quantitative yield. In a related fashion, Lu(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2} (7) was prepared following the reaction of Lu[N(SiMe{sub 3}){sub 2}]{sub 3} with 3 equiv of diisopropylphenol in the presence of THF. The anhydrous trichlorides of Sm, Pr, Gd, and Yb react with 3 equiv of potassium 2,6-diisopropylphenoxide in THF solution to give the 5-coordinate THF bisadducts Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln=Sm(5), Pr (8), Gd (9), Yb (10)). X-ray crystal structures have been obtained for Ln(O-2,6-i-Pr{sub 2}C{sub 6}H{sub 3}){sub 3}(THF){sub 2}(Ln = Er (6), Lu (7), Pr (8), Gd(9)). The four compounds are isostructural, and the molecular structure consists of a distorted trigonal bipyramidal lanthanide metal center with two axial THF and three equatorial aryloxide ligands.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- W-7405-ENG-36
- OSTI ID:
- 420955
- Journal Information:
- Inorganic Chemistry, Vol. 33, Issue 16; Other Information: PBD: 3 Aug 1994
- Country of Publication:
- United States
- Language:
- English
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