Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe3 )2 }3 ]1- Complexes of the Non-traditional +2 Lanthanide Ions.

Abstract

A new series of Ln2+ complexes has been synthesized that overturns two previous generalizations in rare-earth metal reduction chemistry: that amide ligands do not form isolable complexes of the highly reducing non-traditional Ln2+ ions, and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR2 )3 (R=SiMe3 ) complexes in THF under Ar with M=K or Rb in the presence of 2.2.2-cryptand (crypt) forms crystallographically characterizable [M(crypt)][Ln(NR2 )3 ] complexes not only for the traditional Tm2+ ion and the configurational crossover ions, Nd2+ and Dy2+ , but also for the non-traditional Gd2+ , Tb2+ , Ho2+ , and Er2+ ions. Crystallographic data as well as UV/Vis, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4fn 5d1 configurations for Ln2+ ions in this tris(silylamide) ligand environment. The Dy2+ complex, [K(crypt)][Dy(NR2 )3 ], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 μB .