Synthesis and Properties of Some Lanthanoid(III) Perchlorates with Macrocyclic Polythioethers of the -Crown-6 Type. Crystal Structure of Aquadiperchlorato(1,4,10,13-tetraoxa-7,16-dithiacyclo-octadecane)lanthanum(III) Perchlorate

Article abstract of DOI:10.1039/DT9800000376

Some complexes of lanthanoid(III) perchlorates have been prepared with three polythia macrocycles of the <19>-crown-6 type.By using the ligand 1,4,10,13-tetraoxa-7,16-dithiacyclo-octadecane, L¹, in methyl cyanide,three series of complexes have been obtained with formulae (i) Ln3*L¹*H2O (Ln=La, Ce, or Pr) (ii) Ln3*L¹*H2O*xMeCN (Ln=Ce, Pr, Nd, Sm, Eu, Ho, or Yb; x=1.5 or 2), and (iii) Nd3*L¹.The crystal and molecular structure of the title complex has been determined by X-ray diffractometric data.The structure has been refined by least-squares techniques to R=0.036 for 4635 observed reflections.The lanthanum(III) ion is ten-co-ordinated to the six donor atoms of L¹, to two oxygen atoms of a (1-) ion, to an oxygen atom of a second (1-), and to an oxygen atom of a water molecule.The co-ordination polyhedron can be described as a decatetrahedron.The macrocycles 1,10-dioxa-4,7,13,16-tetrathiacyclo-octadecane, L², and 1,4,7,10,13,16-hexathiacyclo-octadecane, L³, do not co-ordinate to lanthanoid(III) perchlorates in methyl cyanide but in dichloromethane the complexes Eu3*L²*H2O and Ln3*L³*H2O (Ln=Sm, Eu, or Yb) can be isolated.The i.r. and electronic spectra of all the complexes are discussed.The electron-transfer transitions are consistent with an optical electronegativity value of 2.8 for ligand L¹ and 2.7 for L² and L³.

Full text of DOI:10.1039/DT9800000376

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