Developments in functionalization of macrocyclic polyamines

Abstract

The classical structure of macrocyclic polyamines (e.g. cyclam 1) have been renovated by means of (1) conversion of amines into amides (i.e. dioxocyclam); (2) replacement of N donors for S donors; (3) replacement of skeletonic C-H for C-F; and (4) attachment of intramolecular pendant donors. The characteristics of dioxocyclam 2 is best illustrated by its ability to incorporate Pt II, while the oxo-free cyclam 1 fails to do so. A new version of dioxocyclam 3 containing two S donors in place of N donors of 2 was designed, which astonishingly selectively accommodates noble metal ions Pt II and Pd II, but not Cu II, Ni II, or Co II as 2 does. Furthermore, 3 detracts Pt II much more rapidly than 2 from cis-[Pt II (NH 3) 2 cl 2]. The fluorinated polyamines show lower N basicities than nonfluorinated counterparts, and yet, the Cu II complex of 21c (CuH -2 L) is more stable than that of 2. The fluorinated polyamine complexes stabilize metal ions with lower oxidation states than nonfluorinated counterparts. Intramolecular pendant donors greatly affect the redox and other chemical properties of the central metal ions, as well as the complex properties. © 1989 IUPAC