SCHEDULED MAINTENANCE
Homoleptic anionic aryloxolanthanoid(III) complexes
Abstract
Several anionic complexes of lanthanoid metals with the
2,6-diphenylphenolate ligand have been synthesized and their
room-temperature single-crystal structures determined. In novel
reactions of anhydrous LnCl
3
(Ln = Nd or Er)
with NaOC
6
H
3
Ph
2
-2,6·0.5thf
(thf = tetrahydrofuran) in
1,3,5-tri-tert-butylbenzene at 300 °C, complexes of
the type
[Na{Ln(OC
6
H
3
Ph
2
-2,6)
4
}] were obtained. Crystallisation of
[Na{Nd(OC
6
H
3
Ph
2
-2,6)
4
}] from bis(2-methoxyethyl) ether (diglyme) or 1,2-dimethoxyethane
(dme) afforded the corresponding solvated complexes
[Na(diglyme)
2
][Nd(OC
6
H
3
Ph
2
-2,6)
4
] or
[Na(dme)
3
][Nd(OC
6
H
3
Ph
2
-2,6)
4
] respectively, and from an analogous reaction for
Ln = Er
[Na(diglyme)
2
][Er(OC
6
H
3
Ph
2
-2,6)
4
] was isolated. The complexes
[Na(diglyme)
2
][Ln(OC
6
H
3
Ph
2
-2,6)
4
] (Ln = Nd or Er) are isomorphous. Their
structures revealed novel discrete homoleptic
tetrakis(aryloxo)lanthanoid(III) anions, well separated from
the solvated sodium cations. Annealing the reaction mixture for the
synthesis of
[Na{Nd(OC
6
H
3
Ph
2
-2,6)
4
}] at 120 °C gave single crystals of a monomeric
bimetallic in which the sodium ion is encapsulated by three aryloxide
oxygens as well as by three phenyl rings of the phenolate ligand, and
neodymium is surrounded by a highly distorted tetrahedral arrangement of
aryloxide oxygens. There are also intramolecular π-Ph–M
(M = Na or Nd) interactions.
Please wait while we load your content...
