ISSN:
0009-2940
Keywords:
Metal(II) complexes mono- and dinuclear
;
Schiff bases, macrocyclic
;
Redox properties
;
Superexchange interactions of d9 systems
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Complexes with Macrocyclic Ligands, III[1]. - Mono- and Dinuclear Macrocyclic Transition Metal Complexes of Ligands of Schiff Base Type: Syntheses, Structures, Electro- and Magnetochemical Properties.Four new mononuclear metal(II) complexes (4a-d) of a macrocyclic ligand derived from the Schiff base condensation of 2 equiv. of 1,2-phenylenediamine (3a) and 5-tert-butyl-2-hydroxy-1,3-benzenedicarbaldehyde (2) were synthesized and the cobalt complex 4b characterized by X-ray structure analysis. Reaction of 1,2-diamino-3,4,5,6-tetrafluorobenzene (3b) with the dicarbaldehyde 2 in the presence of Mn(ClO4)2 or Co(ClO4)2 leads to the novel metal-free macrocyce 6 (X-ray structure determination). The macrocycle 6 and Cu(ClO4)2 yield the new dinuclear copper complex 8, the structure of which was also determined by X-ray diffraction. The copper-(II) ions in 8 have a distorted square-pyramidal coordination by the four donor atoms of the macrocycle and an apical acetonitrile ligand. The Cu…Cu distance is 318.1 pm, and the two Cu(II) ions show only a small antiferromagnetic exchange interaction of J= -41 cm-1. Another new dinuclear Cu(II) complex (10) of a macrocyclic ligand derived from the Schiff base condensation of 2,2′-diaminooctafluorobiphenyl (9) and dicarbaldehyde 2 was synthesized and characterized by X-ray structure analysis, electrochemical investigations (DCV), and variable-temperature magnetic susceptibility measurements. One copper ion in complex 10 is five-coordinate (square-pyramidal), the other one six-coordinate (distorted octahedral). The Cu…Cu distance is 301.5 pm and the antiferromagnetic coupling J= -774 cm-1.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941271002
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