copper(ii) complexes of binucleating macrocyclic bis(disulfide)tetramine ligands
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28 ABSTRACTS
L24 COPPER(I1) COMPLEXES OF BINUCLEATING MACROCYCLIC BIS(DISULFIDE)TETRAMINE LIGANDS
, Stephen Fox, Joseph Potenza, Spencer Knapp, Barvev SC-
Department of Chemistry, Rutgers-The State University of New Jersey, New Brunswick, New Jersey 08903 USA
Novel structural features such as substantial Cu(II)-S(disulfide) bonding and disulfide-bridging of Cu(I1) ions can be enforced by the macrocyclic bis(disulfide)tetramine l&and 3a. The isostructural Cu(II) and Ni(II) dimers 2a,b were prepared in good yield as the CH$N-solvated iodide salts by oxidative coupling of the stable cis-(M(II)N$32 monomers la,b with 12. The free ligands 3a,b were obtained by displacement of Ni(I1).
la,b
I2 CH&N
t
M - Cu’ Ni” - I
L= NCCH3 2a,b
73 CJ . 2 I-
CH3CN H20 _
3a,b
a series: R =
4a
b series: R =
The Cu(I1) coordination geometry, strength of the Cu-disulfide interaction, and a bridging or non-bridging role of the disulfides depends upon the size of the macrocycle and the nature of the counterions (iodide vs cyanate). Structural, spectroscopic, and magnetochemical properties of these dimers will be presented.