A study has been made of the application of the dianion of the fluorinated alcohol-thioether 2,2'-[thiobis(methylene)]bis-[ 1,1,1,3,3,3-hexafluoro-2-propanol], [HOC(CF3)2CH2]2S, as a tridentate, dinegative, ligand. Stable, neutral, complexes are formed with Coz+, Ni2+, and Cu2+ from nitrogen-containing coligands, and five-wordination is favored. A complete structural determination has been carried out on the complex Co[OC(CF )2CH2]2S(C5H~N)2. The crystals are monoclinic, space group C2/c, with a = 26.24 (1) A, b = 16.565 (9) A, c = 10.998 (6) A, 0 = 104.50 (4)O, and 2 = 8. The Co2+ ion is five-coordinate in trigonal-bipyramidal geometry, with the alkoxy-thioether ligand adopting a facial configuration, the sulfur atom being in the apical position. These complexes show no tendency to increase the coordination number of the metal to 6 by solvation, an effect attributed to the bulk of the fluorinated alkoxy groups.

Der wie aufgezeigt synthetisierte Ligand (III) liefert mit den entsprechenden Metall? chloriden Komplexe, in denen er als dreizähniger, dinegativer Ligand fungiert.