Characterization and reactivity of peralkylated LnIIAlIII heterobimetallic complexes

• Published in: Dalton transactions : an international journal of inorganic chemistry 2008-04 (14), p.1899-1907
• Main Authors: Sommerfeldt, Hanne-Marthe, Meermann, Christian, Schrems, Marcus G, Törnroos, Karl W, Frøystein, Nils Age, Miller, Robert J, Scheidt, Ernst-Wilhelm, Scherer, Wolfgang, Anwander, Reiner
• Format: Article
• Language: English
• Subjects: Aluminum - chemistry; Crystallography, X-Ray; Lanthanoid Series Elements - chemistry; Magnetic Resonance Spectroscopy - methods; Magnetic Resonance Spectroscopy - standards; Models, Molecular; Molecular Conformation; Organometallic Compounds - chemical synthesis; Organometallic Compounds - chemistry; Reference Standards; Stereoisomerism
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/b716603f

The heterobimetallic peralkylated complexes [Ln(AlR4)2]n (Ln = Sm, Yb; R = Me, Et) were synthesized by a silylamide elimination route from Ln[N(SiMe3)2]2(THF)2 and an excess of AlR3. The solid-state structure of [Sm(AlEt4)2]n is isomorphous to that of the ytterbium derivative. Polymeric [Yb(AlMe4)2]n was examined by 1H and 13C MAS NMR spectroscopy revealing the presence of distinct bridging methyl groups. The reaction of [Yb(AlMe4)2]n and 1,10-phenanthroline (Phen) afforded the monomeric donor adduct Yb(AlMe4)2(Phen), while the protonolysis reaction with 2 equiv. C5Me5H (HCp*) yielded a separated ion pair of composition [Cp*Yb(THF)(4)][AlMe(4)]. Single-crystal X-ray diffraction data are provided for both ytterbium(II) complexes. Solid-state magnetic measurements (SQUID) were performed on [Sm(AlMe4)2]n, [Sm(AlEt4)2]n, SmI2(THF)2 and Sm[N(SiMe3)2]2(THF)2 showing high effective magnetic moments 3.67micro(B) < micro(eff) < 4.43micro(B).