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- Title
Synthesis and Characterization of C-meso and C-racemic Isomers of a Reinforced Tetraaza Macrocycle and Their Copper(II) Complexes.
- Authors
Gyeong Rok Jeong; Juyoung Kim; Shin-Geol Kang; Jong Hwa Jeong
- Abstract
Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[10.2.25.8]- octadecane (L²) containing additional N-CH2CH2-N linkages, C-meso-L² and C-racemic-L2, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-L¹ or C-racemic-L¹ (L¹ = 5,5,7,12,12,14- hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-L² and C-racemic-L² react with copper(II) ion to form [Cu(C-meso-L²)]2+ or [Cu(C-racemic-L²)]2+ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-L²)(H2O)](ClO4)2 shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) Å] of [Cu(C-racemic-L²)(H2O)](ClO4)2 are longer than those [1.992(3)- 2.000(3) Å] of [Cu(C-racemic-L¹)(H2O)](ClO4)2. As a result, [Cu(C-racemic-L²)(H2O)]2+ exhibits weaker ligand field strength than [Cu(C-racemic-L1)(H2O)]2+. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex [Cu2(C-meso-L²)2CN]3+ or [Cu2(C-racemic-L²)2CN]3+. Spectra and chemical properties of [Cu(C-meso-L²)]2+ and [Cu2(C-meso-L²)2CN]3+ are not quite different from those of [Cu(C-racemic-L²)]2+ and [Cu2(C-racemic-L²)2CN]3+, respectively.
- Subjects
ISOMER synthesis; MACROCYCLIC compounds; COPPER compounds; COMPLEX compounds; CRYSTAL structure
- Publication
Bulletin of the Korean Chemical Society, 2014, Vol 35, Issue 7, p2043
- ISSN
0253-2964
- Publication type
Article
- DOI
10.5012/bkcs.2014.35.7.2043