ISSN:
0009-2940
Keywords:
Copper(I) complexes
;
Copper(II) complexes
;
N,S-Donor ligands
;
Macrocyclic ligands
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The synthesis and characterization of seven copper coordination compounds with the 14-membered macrocyclic cis-N2S2 dibenzo ligand 6,7,13,14,15,16,17,18-octahydrodibenzo[e,m]-[1,4,8,11]dithiadiazacyclotetradecine (L1) and its N,N'-bisacetato and -bis(methylpyridyl) functionalized derivatives H2L2 and L3 are described. The structures of five compounds were determined by single-crystal X-ray diffraction. The tetrahedrally distorted square-planar coordination geometry of [CuL1](ClO4)2 (1) changes upon reduction of copper to a severely distorted tetrahedral geometry in [CuL1]Br · MeCN (2). The Cu-N bond lengths increase from 1.988(3) to 2.029(5) Å; the Cu-S bond lengths decrease from 2.293(1) to 2.255(2) Å. Copper(II) is hexacoordinated in [CuHL2]HSO4 · 2.5 H2O (5) and [CuHL2]ClO4 · H2O (6). Both compounds exhibit very similar overall structures in the cationic part. The macrocyclic ring of the ligand is folded along an N⃜S axis, the octahedral geometry is strongly Jahn-Teller distorted, with O and S donor atoms in the apical positions. Compound 5 contains one very short [2.271(3) Å] and one long [2.701(3) Å] Cu-S (thioether) bond. In [CuL3](ClO4)2 · 2 H2O (7) one thioether group of the ligand L3 remains uncoordinated. The coordination polyhedron is rather irregular: Cu-S 2.506(3) and Cu-N 1.960(7)-2.107(8) Å. The compounds were further characterized by electronic and EPR spectroscopy and by cyclic voltammetry. Some relationships to the structural and spectroscopic properties of “blue” copper proteins were found.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951281211
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