The Syntheses, Properties, and Crystal and Molecular Structures of the Lanthanoid Mixed-Complexes of <i>O</i>,<i>O</i>′-Diisopropyl Dithiophosphate and Dimethyl Sulfoxide: [Ln{(C3H7O)2PS2}3{(CH3)2SO}2] (Ln=La or Nd), and [Eu{(C3H7O)2PS2}2{(CH3)2SO}3][Eu{(C3H7O)2PS2}4]

Abstract

Abstract Two types of the mixed complexes indicated in the title have been synthesized, and their crystal and molecular structures of the lanthanum (1) and the europium (2) complexes have been determined by the X-ray diffraction method. Both 1 and 2 are monoclinic, space group P21⁄n, and Z=4. 1, a=17.354(7), b=23.336(4), c=10.955(2) Å, β=96.04(2)°, final R value calculated from 4870 reflections is 0.069; 2, a=29.846(7), b=20.070(3), c=14.057(3) Å, β=92.13(2)°, final R value calculated from 7811 reflections is 0.077. In 1, the central metal atom is octa-coordinated, and is in a dodecahedral geometry, where all O,O′-diisopropyl dithiophosphato ligands (iPr2dtp) span m-edges of the dodecahedron, chelating through both of the respective sulfur atoms. Dimethyl sulfoxide (dmso) ligands occupy the apexes of the other m-edge. In 2, the europium(III) metal atom of the cationic species is hepta-coordinated and is in a pentagonal-bipyramidal geometry where two oxygen atoms of dmso ligate from respective ends of the axis and one oxygen atom of the remaining dmso from the equatorial direction. The central metal atom of the anion is octa-coordinated and is in a dodecahedron; where all m-edges are spanned by iPr2dtp ligands. The solid and the acetonitrile solution of 2 is orange in color due to the charge-transfer band (λmax=415 nm; εmax=1.5×102 dm3 mol(Eu)−1 cm−1).