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Synthesis, Structure, and Magnetism of Tris(amide) [Ln{N(SiMe 3 ) 2 } 3 ] 1− Complexes of the Non‐traditional +2 Lanthanide Ions
Author(s) -
Ryan Austin J.,
Darago Lucy E.,
Balasubramani Sree Ganesh,
Chen Guo P.,
Ziller Joseph W.,
Furche Filipp,
Long Jeffrey R.,
Evans William J.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800610
Subject(s) - lanthanide , magnetism , ion , amide , tris , crystallography , chemistry , inorganic chemistry , physics , condensed matter physics , organic chemistry , biochemistry
A new series of Ln 2+ 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 Ln 2+ ions, and that yttrium is a good model for the late lanthanides in these reductive reactions. Reduction of Ln(NR 2 ) 3 (R=SiMe 3 ) 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(NR 2 ) 3 ] complexes not only for the traditional Tm 2+ ion and the configurational crossover ions, Nd 2+ and Dy 2+ , but also for the non‐traditional Gd 2+ , Tb 2+ , Ho 2+ , and Er 2+ ions. Crystallographic data as well as UV/Vis, magnetic susceptibility, and density functional theory studies are consistent with the accessibility of 4f n 5d 1 configurations for Ln 2+ ions in this tris(silylamide) ligand environment. The Dy 2+ complex, [K(crypt)][Dy(NR 2 ) 3 ], has a higher magnetic moment than previously observed for any monometallic complex: 11.67 μ B .