Redox-induced ligand reorganization and helicity inversion in copper complexes of N,N-dialkylmethionine derivatives.
N,N'-Dipicolyl, bis(stilbylvinylpyridylmethyl), and diquinaldyl methionine derivatives form stable Cu(II) complexes with metal ligation by three nitrogen atoms and the carboxylate. One-electron reduction results in the exchange of carboxylate for sulfide in the complexes. This ligand reorganization is accompanied by inversion of the helical orientation of the two arms containing nitrogen heterocycles, resulting in nearly mirror image circular dichroism spectra. This paper provides details for the synthesis of these complexes and the evidence for the remarkable stereochemical interconversion that accompanies the reduction reaction. Detailed analysis of the electronic spectra of the ligands and metal complexes is provided along with X-ray crystallographic structures of Cu(II) and Zn(II) complexes of the N,N'-dipicolylmethionine complexes.
Zahn
Steffen
S
Department of Chemistry, New York University, New York, NY 10003, USA.
Das
Debasis
D
Canary
James W
JW