Lanthanide(II) Complexes Supported by N,O-Donor Tripodal Ligands: Synthesis, Structure, and Ligand-Dependent Redox Behavior.
The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O-donor tripodal ligands (tris(2-pyridylmethyl)amine (TPA), BPA(-) (HBPA=bis(2-pyridylmethyl)(2-hydroxybenzyl)amine), BPPA(-) (HBPPA=bis(2-pyridylmethyl)(3.5-di-tert-butyl-2-hydroxybenzyl)amine), and MPA(2-) (H2 MPA=(2-pyridylmethyl)bis(3.5-di-tert-butyl-2-hydroxybenzyl)amine) is reported. The X-ray crystal structures of the heteroleptic Ln(2+) complexes [Ln(TPA)I2 ] (Ln=Eu, Yb) and [Yb(BPA)I(CH3 CN)]2 , of the Ln(2+) homoleptic [Ln(TPA)2 ]I2 (Ln=Sm, Eu, Yb) and [Eu(BPA)2 ] complexes, and of the Ln(3+) [Eu(BPPA)2 ]OTf and [Yb(MPA)2 K(dme)2 ] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis-ligand complexes of Eu(3+) and Yb(3+) show that the metal center reduction occurs at significantly lower potentials for the BPA(-) ligand as compared with the TPA ligand. This suggests that the more electron-rich character of the BPA(-) ligand results in a higher reducing character of the lanthanide complexes of BPA(-) compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis-TPA complexes of Eu(2+) and Yb(2+) do not show any reactivity with heteroallenes, the [Eu(BPA)2 ] complex reduces CS2 to afford the first example of a lanthanide trithiocarbonate complex.
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland).
Julie
J
Andrez
Univ. Grenoble Alpes, INAC-SCIB, F-38000 Grenoble, France, CEA, INAC-SCIB, 38000 Grenoble (France).
Gülay
G
Bozoklu
Univ. Grenoble Alpes, INAC-SCIB, F-38000 Grenoble, France, CEA, INAC-SCIB, 38000 Grenoble (France).
Grégory
G
Nocton
Univ. Grenoble Alpes, INAC-SCIB, F-38000 Grenoble, France, CEA, INAC-SCIB, 38000 Grenoble (France).
Jacques
J
Pécaut
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland).
Rosario
R
Scopelliti
Univ. Grenoble Alpes, INAC-SCIB, F-38000 Grenoble, France, CEA, INAC-SCIB, 38000 Grenoble (France).
Lionel
L
Dubois
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne (Switzerland). marinella.mazzanti@epfl.ch.
Marinella
M
Mazzanti
europium; lanthanides; ligands; reduction; ytterbium