Redox-iduced ligand reorganization and helicity inversion in copper complexes of N,N-dialkylmethionine derivatives

Steffen Zahn, Debasis Das, James Canary

Research output: Contribution to journalArticle

Abstract

N,N′-Dipicolyl, bis(stilbylvinylpyridylmethyl), and diquinaldyl methionine derivatives form stable CuII 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 CuII and ZnII complexes of the N,N′-dipicolylmethionine complexes.

Original languageEnglish (US)
Pages (from-to)6056-6063
Number of pages8
JournalInorganic Chemistry
Volume45
Issue number15
DOIs
StatePublished - Jul 24 2006

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carboxylates
Copper
Nitrogen
inversions
Ligands
Derivatives
copper
methionine
ligands
Coordination Complexes
Dichroism
Sulfides
electronic spectra
Methionine
metals
nitrogen atoms
dichroism
sulfides
Ion exchange
Mirrors

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Redox-iduced ligand reorganization and helicity inversion in copper complexes of N,N-dialkylmethionine derivatives. / Zahn, Steffen; Das, Debasis; Canary, James.

In: Inorganic Chemistry, Vol. 45, No. 15, 24.07.2006, p. 6056-6063.

Research output: Contribution to journalArticle

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AB - N,N′-Dipicolyl, bis(stilbylvinylpyridylmethyl), and diquinaldyl methionine derivatives form stable CuII 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 CuII and ZnII complexes of the N,N′-dipicolylmethionine complexes.

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