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Ein‐ und zweikernige makrocyclische Übergangsmetallkomplexe mit Liganden vom Schiff‐Basen‐Typ: Synthesen, Strukturen, elektro‐ und magnetochemische Eigenschaften
Author(s) -
Brychcy Klaus,
Dräger Klaus,
Jens KlausJ.,
Tilset Mats,
Behrens Ulrich
Publication year - 1994
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19941271002
Subject(s) - chemistry , square pyramidal molecular geometry , schiff base , ligand (biochemistry) , crystallography , acetonitrile , macrocyclic ligand , copper , octahedron , metal , magnetic susceptibility , stereochemistry , cobalt , crystal structure , inorganic chemistry , organic chemistry , biochemistry , receptor
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(ClO 4 ) 2 or Co(ClO 4 ) 2 leads to the novel metal‐free macrocyce 6 (X‐ray structure determination). The macrocycle 6 and Cu(ClO 4 ) 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 .