Copper(II) complexes of open-chain thioether ligands terminated by salicylaldimine functionality

From 1,11-bis(salicylaldimine)-3,6,9-trithiaundecane ([H.sub.2]LI), 1,11-bis(salicylaldimine)-6-oxa-3,9-dithiaundecane ([H.sub.2]L2), and 1,8-bis(salicylaldimine)-3,6-dithiaundecane ([H.sub.2]L3), syntheses for [[Cu(L1)].sub.2] (I), Cu(L2)*C[H.sub.3]OH (II), Cu(L3) (III), [Cu(HL3)][C[H.sub.3]COO] (IV), [Cu(HL1-sal)][Cl.sub.2] (V), [Cu.sub.4][(L1).sub.2][Br.sub.4][([H.sub.2][O.sub.2]).sub.2]*2[H.sub.2]O(VI) and [Cu.sub.2](L2)[Br.sub.2]*x[H.sub.2]O(VII) are described. Single crystal X-ray structural studies for I, III and VII are reported. Variable temperature magnetic susceptibility studies of I, VI and VII are discussed. The examination of VII represents the first magneto-structural study of a binuclear copper(II) species with NS[O.sub.3]Br coordination spheres. This study examines perturbation by one or more of the donor atoms so that none of the known magnetostructural models predicts the copper-copper coupling. Key words: binuclear copper(II) complexes, thioether, salicylaldimine ligands, variable temperature magnetic susceptibility, magnetostructural correlation, X-ray structure. Utilisant les 1,11-bis(salicylaldimine)-3,6,9-trithiaundecane ([H.sub.2]L1), 1,11-bis(salicylaldimine)-6-oxa-3,9- dithiaundecane ([H.sub.2]L2) et 1,8-bis(salicylaldimine)-3,6-dithiaundecane ([H.sub.2]L3), on a realise les syntheses des complexes [[Cu(L1)].sub.2] (I), Cu(L2>C[H.sub.3]OH (II), Cu(L3) (III), [Cu(HL3)][C[H.sub.3]COO] (IV), [Cu(HLI-sal)][Cl.sub.2] (V), [Cu.sub.4][(L1).sub.2]Brs[([H.sub.2][O.sub.2]).sub.2]*2[H.sub.2]O(VI)et [Cu.sub.2](L2)[Br.sub.2]*x[H.sub.2]O(VII). On a effectue la determination des structures des composes I, III et VII par diffraction des rayonsX sur un cristal unique. On discute des resultats d'etudes de susceptibilite magnetique des composes I, VI et VII, a temperature variable. L'examen du compose VII correspond a la premiere etude magneto-structurale d'une espece de cuivre(II) binucleaire comportant des spheres de coordination avec du NS[O.sub.3]Br. Cette etude permet d'examiner la perturbation par un ou plusieurs atomes donneurs; aucun des modeles magneto-structuraux ne predit le couplage cuivre-cuivre. Mots-cles : complexes de cuivre(II) binucleaire, thioether, ligands salicylaldimine, susceptibilite magnetique a temperature variable, correlation magneto-structurale, structure par diffraction des rayons X. [Traduit par la Redaction]
Introduction Magnetostructural correlations involving multinuclear metal complexes remain of interest. (1-5) Although the nuclearity of complexes being reported continues to rise, (6,7) much that is of fundamental significance can be [...]