ISSN:
0009-2940
Schlagwort(e):
Macrocycles
;
Hydrogenation
;
Cyclam, binding constant
;
N ligands
;
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
We report here a new synthetic route to highly-substituted tetraazamacrocycles. Raney nickel hydrogenation of macrocyclic phenylenediamine-acetylacetone condensation products gives cyclams in high yield with complexes all-cis stereoselectivity. The extensive C-substitution of the cyclam 2a changes its ligand properties markedly. The X-ray structure analyses of NiII, CuII, and ZnII complexes of 2a reveals a deviation of the metal ion coordination geometry from the usual square-planar arrangement. This may account for the differences in the redox properties of the NiII and CuII complexes of 2a leads to more positive oxidation and reduction potentials compared to the analogous unsubstituted cyclam complexes. While the binding constant between Zn(ClO4)2 and 2a is lower by a factor of 105 compared to cyclam, the subsequent binding of uridine to the zinc-cyclam complexes in methanol/water is slightly stronger in the case of 2a · Zn(ClO4)2].
Zusätzliches Material:
6 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19971300412
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