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Complexes macrocycliques des lanthanides: Stabilité et comportement électrochimique dans le méthanol et le carbonate de propylène

✍ Scribed by Marie-Christine Almasio; Françoise Arnaud-Neu; Marie-José Schwing-Weill

Publisher
John Wiley and Sons
Year
1983
Tongue
German
Weight
642 KB
Volume
66
Category
Article
ISSN
0018-019X

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✦ Synopsis

Macrocyclic Complexes of Lanthanides: Stability and Electrochemical Behaviour in Methanol and Propylene Carbonate

The stabilities of the 1:1 complexes of the trivalent lanthanides with the diazapolyoxamacrocycles (2.1.) and (2.2.1.) in anhydrous methanol and propylene carbonate have been determined at 25°, by competitive potentiometric methods using H^+^ or Ag^+^ as auxiliary cations, with Et~4~NClO~4~ as supporting‐electrolyte. Additional data are also reported for the crown ethers 15C5 and 18C6 in propylene carbonate.

It is shown that the diazapolyoxamacrocycles are much stronger complexing agents for trivalent lanthanides than macrocyclic polyethers, and that the bicyclic (2.2.1.) cryptates are more stable than the monocyclic (2.1.) complexes. With increasing atomic number of the lanthanides, the stability increases with diazapolyoxamacrocycles and decreases with cyclic polyethers.

The electrochemical reduction of the trivalent samarium and europium cryptates has been investigated by polarography on a dropping Hg‐electrode, in water and methanol. In both solvating solvents, the +2 oxidation states of the cations are stabilized by complexation.

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