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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 [...]

Synthesesof 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), and 1,8-bis(salicylaldimine)-3,6-dithiaundecane ([H.sub.2]L3), their nickel complexes [Ni(L1)]*[H.sub.2]O(I), [Ni(HL2)][OAc] (II), [[Ni(L3)-HOAc].sub.2][Ni(L3)-2HOAc]*3[H.sub.2]O (III), [Ni(HL1-sal)][Cl.sub.2]*[H.sub.2]O(IV), [Ni(HL2-sal)][Cl.sub.2]*C[H.sub.3]OH (V), [Ni(L3-sal)Cl]*[H.sub.2]O(VI), [{[Ni(HL1-sal)][Br.sub.2]}.sub.2][Ni(L1-sal)]Br}*[H.sub.2]O(VII), [{[Ni(HL2- sal)][Br.sub.2]}.sub.2]{[Ni(L2-sal)]Br}*2C[H.sub.3]OH (VIII), {[Ni(HL3-sal)Br]Br}[Ni(L3-sal)Br]*2C[H.sub.3]OH (IX), [Ni(HL3-sal)Br]Br*C[H.sub.3]OH (X), [Ni(HL3)Br]*2[H.sub.2]O(XI), [[Ni(HL1)].sub.2][[B[F.sub.4]].sub.2]*5[H.sub.2]O(XII), [[Ni(HL2)].sub.2][[B[F.sub.4]].sub.2]*3[H.sub.2]O(XIII), [Ni(HL3)MB[F.sub.4]]2*C[H.sub.3]CN (XIV), and [Ni(HL3)MB[F.sub.4]]2*3[H.sub.2]O (XV) and their cobalt complexes [Co(L1-sal)][[B[F.sub.4]].sub.2] (XVI), [Co(L2)][OAc]*3[H.sub.2]O(XVII), [Co(L3)][OAc]*3[H.sub.2]O(XVIII), [Co(L3)][B[F.sub.4]](XIX), and [Co(L3-sal)(C[H.sub.3]OH)][[B[F.sub.4]].sub.2]*C[H.sub.3]OH (XX) are reported. Single crystal X-ray structural studies for III, XIV, XVI, and XIX are described. Cyclic voltammogramsof the ligands andof I, II, III, VII, VIII, X, XIV, and XIX are discussed. Electronic spectraof the ligands and complexes are discussed. Key words: cobalt and nickel complexes, thioether, salicylaldimine ligands, X-ray structure, cyclic voltammetry, UV-vis spectra. On decrit les syntheses du 1,11-bis(salicylaldimine)-3,6,9-trithiaundecane ([H.sub.2]L1), 1,11-bis(salicylaldimine)-6- oxa3,9-dithiaundecane ([H.sub.2]L2) et du 1,8-bis(salicylaldimine)-3,6-dithiaundecane ([H.sub.2]L3), de leurs complexes de nickel [Ni(Ll)]- [H.sub.2]O (I), [Ni(HL2)][OAc] (II), [[Ni(L3)-HOAc].sub.2][Ni(L3)-2HOAc]*3[H.sub.2]O(III), [Ni(HL1-sal)][Cl.sub.2]*[H.sub.2]O(IV), [Ni(HL2-sal)][Cl.sub.2]-C[H.sub.3]OH (V), [Ni(L3-sal)Cl]*[H.sub.2]O(VI), {[Ni(HL1-sal)][Br.sub.2]M[Ni(L1-sal)]Br}*[H.sub.2]O(VII), {[Ni(HL2- sal)][Br.sub.2]h{[Ni(L2-sal)]Br}*2C[H.sub.3]OH (VIII), {[Ni(HL3-sal)Br]Br}2[Ni(L3-sal)Br]*2C[H.sub.3]OH (IX), [Ni(HL3-sal)Br]Br*C[H.sub.3]OH (X), [Ni(HL3)Br]*2[H.sub.2]O(XI), [Ni(HL1)MB[F.sub.4]]2*5[H.sub.2]O(XII), [Ni(HL2)2[[B[F.sub.4]].sub.2]*3[H.sub.2]O(XIII), [Ni(HL3MB[F.sub.4]]2- C[H.sub.3]CN (XIV) et [Ni(HL3)2MB[F.sub.4]]2-3[H.sub.2]O (XV) ainsi que de leurs complexes de cobalt [Co(L1-sal)][[B[F.sub.4]].sub.2] (XVI), [Co(L2)][OAc]-3[H.sub.2]O(XVII), [Co(L3)][OAc]-3[H.sub.2]O (XVIII), [Co(L3)][B[F.sub.4]](XIX) et [Co(L3-sal)(C[H.sub.3]OH)][[B[F.sub.4]].sub.2]*C[H.sub.3]OH (XX).on decrit les structures des composes III, XIV, XVI et XIX telles que determinees par diffraction des rayons-X.on discute des resultatsobtenus par voltamperometrie cyclique des ligands I, II, III, VII, VIII, X, XIV et XIX.on discute aussi des spectres electroniques des ligands et des complexes. Mots-cles : complexes du cobalt et du nickel, thioether, ligands de la salicylaldimine, structure par diffraction des rayons X, voltamperometrie cyclique, spectres UV-visible. [Traduit par la Redaction], Introduction Metal complexes of salicylaldimine ligands continue to be of interest for several reasons, not the least of which is their potential for use in a variety of applications such [...]