The chiral and bulky tacn (1,4,7-triazacyclononane, L-1) analogue chtacn (2
,5,8-triazabicyclo[7.4.0(1,9)]tridecane, L-2), which has a cyclohexane ring
fused to the tacn framework, has been synthesized commencing with (+/-), (
+)- or (-)-trans-cyclohexane-1,2-diamine. Syntheses and properties of cobal
t(III), nickel(II), chromium(III) and iron(III) complexes are described. In
the complex bis(RR-2,5,8-triazabicyclo[7.4.0(1,9)]tridecane)cobalt(III) ch
loride hexafluorophosphate the cyclohexane rings and pairs of adjacent seco
ndary amines occupy an approximate plane around the cobalt ion, with the re
maining secondary amines in each tridentate ligand in trans dispositions. A
large positive Cotton effect occurs under the low energy absorption band i
n the circular dichroism spectrum of this cobalt(III) complex of the R,R-(-
)-chtacn ligand. In the dinuclear complex aqua-di-mu-chloro-chlorobis(SS-2,
5,8-triazabicyclo[7.4.0(1,9)]tridecane)dinickel(II) perchlorate each nickel
atom is bound to a tridentate macrocyclic ligand in different dispositions
, with the distorted octahedron of each nickel completed by two bridging ch
loride ions and either a chloride ion or aqua molecule. For [M(L-n)(2)](n+)
complexes, electronic maxima are shifted slightly to lower energy and redu
ction potentials slightly to more negative potential in the case of L-2 com
pared with L-1.