Dramatic enhancement of the stability of rare-earth metal complexes with alpha-methyl substituted N,N-dimethylbenzylamine ligands

作者：Petrov Alex R; Thomas Oliver; Harms Klaus; Rufanov Konstantin A; Sundermeyer Joerg^*

来源：Journal of Organometallic Chemistry, 2010, 695(25-26): 2738-2746.

DOI：10.1016/j.jorganchem.2010.09.042

• Rare-earth metals
• Yttrium
• Samarium
• Neodymium
• Dysprosium
• Lutetium

Stepwise substitution of benzylic CH(2) protons in ortho-metallated N,N-dimethylbenzylamine (dmba) ligands leads to chiral ortho-metallated N,N,alpha-trimethylbenzylamine (tmba) and cumyl-N,N-dimethylamine (cuda) ligands. These larger ligands with less or no acidic protons in benzylic position prove to stabilize some of those homoleptic tris-aryls of the larger (middle) and largest (early) rare-earth metal cations, for which such tris-aryl or tris-dmba complexes could not be synthesized so far. The syntheses, characterization and crystal structures of [Li(cuda)], [(tmba)(2)Lu(mu-Cl)](2) (1), [(tmba)(2)Y(mu-Cl)](2) (2), [Y (tmba)(3)] (3), [Dy(tmba)(3)] (4), [Nd(tmba)(3)] (5), [Sm(tmba)(3)] (6), and [Sm(cuda)(3)] (7) are reported, trends in complex stability are discussed.

• 出版日期2010-12