Coordination of imidazoles by Cu(II) and Zn(II) as studied by NMR relaxometry, EPR, far-FTIR vibrational spectroscopy and ab initio calculations

effect of methyl substitution

Markus Andersson*, Jesper Hedin, Patrik Johansson, Jonas Nordström, Magnus Nydén

*Corresponding author for this work

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Synthetic imidazole ligands are typically substituted at the N1 ((1)-Im) position while natural imidazole ligands are substituted at the C 4 ((4)-Im) position. To outline the difference in coordination properties, the methyl-substituted imidazoles Me(4)-Im and Me(1)-Im were complexed with CuCl2 and ZnCl2 and investigated by NMR relaxometry, electron paramagnetic resonance, far-Fourier transform IR vibrational spectroscopy, and ab initio calculations. Me(4)-Im, Me(1)-Im, and Im in excess form the usual tetragonal D4h [CuL4X 2] complexes with CuCl2 whereas the methylated imidazoles form pseudotetrahedral C2v complexes instead of the usual octahedral Oh [ZnIm6]2+ complex. All imidazoles display a high degree of covalence in the M-L σ- and π-bonds and the π-interaction strength affects the relative energies of complexation. Opportunities to tailor complexes by the chemical properties of the substituents are envisaged due to the role of the inductive and hyperconjugative effects, rather than position.

Original languageEnglish
Pages (from-to)13146-13153
Number of pages8
JournalJournal of Physical Chemistry A
Volume114
Issue number50
DOIs
Publication statusPublished - 23 Dec 2010
Externally publishedYes

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