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Synthesis and Characterization of Copper, Nickel and Cobalt Complexes ofN,N′-Dimethyl-2,11-diaza[3,3](2,6)pyridinophane

✍ Scribed by Krüger, Hans-Jörg

Publisher
Wiley (John Wiley & Sons)
Year
1995
Tongue
English
Weight
1021 KB
Volume
128
Category
Article
ISSN
0009-2940

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✦ Synopsis

The properties of the tetraazamacrocyclic compound N,N 'dimethyl-2,11 -diaza[ 3,3] (2,G)pyridinophane (L-N4Mez) as a ligand for some selected metal chlorides have been examined. The crystal structure of the uncoordinated ligand reveals a syn chair-chair conformation. In solution, the ligand displays fluctional behavior. Reaction of L-N4Mez with the chlorides of copper(II), nickel(II), and cobalt(I1) affords the com-

. HzO (4), and [Co(L-N4Me2)Cl2] . 2 HzO (5) in which the ligand adopts a syn boat-boat conformation. The crystal structures of 4 and 5 are presented. Due to the small cavity of the 12-membered ring of the ligand, exclusively distorted cis-octahedral coordination geometries are found at the metal sites. A comparison of structural data of several complexes with this ligand shows that the extent of the distortions from ideal octahedral geometry is mainly determined by the M-N,, bond strength. The electronic as well as the solution properties of the described complexes have been investigated by electronic absorption spectroscopy, ESR spectroscopy, and electrochemical methods.

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