Lanthanide(III) Di- and Tetra-Nuclear Complexes Supported
by a Chelating Tripodal Tris(Amidate) Ligand
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Abstract
Syntheses,
structural, and spectroscopic characterization of multinuclear tris(amidate)
lanthanide complexes is described. Addition of K<sub>3</sub>[N(<i>o</i>-PhNC(O)<i><sup>t</sup></i>Bu)<sub>3</sub>] to LnX<sub>3</sub> (LnX<sub>3</sub> = LaBr<sub>3</sub>, CeI<sub>3</sub>, and NdCl<sub>3</sub>) in <i>N</i>,<i>N</i>-dimethylformamide (DMF) results in the generation of dinuclear complexes,
[Ln(N(<i>o</i>-PhNC(O)<sup><i>t</i></sup>Bu)<sub>3</sub>)(DMF)]<sub>2</sub>(μ-DMF)
(Ln = La (<b>1</b>), Ce (<b>2</b>), Nd(<b>3</b>)),
in good yields. Syntheses of tetranuclear complexes, [Ln(N(<i>o</i>-PhNC(O)<sup><i>t</i></sup>Bu)<sub>3</sub>)]<sub>4</sub> (Ln = Ce (<b>4</b>), Nd(<b>5</b>)), resulted
from protonolysis of Ln[N(SiMe<sub>3</sub>)<sub>2</sub>]<sub>3</sub> (Ln = Ce, Nd) with N(<i>o</i>-PhNCH(O)<sup><i>t</i></sup>Bu)<sub>3</sub>. In the solid-state, complexes <b>1</b>–<b>5</b> exhibit coordination modes of the
tripodal tris(amidate) ligand that are unique to the 4f elements and
have not been previously observed in transition metal systems
