Issue 26, 2021

Pseudotetrahedral copper(ii)-complexes with enantiopure (R or S)-2-(((aryl)ethylimino)ethyl)phenolate Schiff base ligands

Abstract

Condensation of 2-hydroxy-benzophenone (HL′) with (R or S)-(Ar)ethylamine yields the enantiopure Schiff bases (S or R)-2-((E)-1-(1-(Ar)ethylimino)ethyl)phenol {Ar = C6H5 (S- or R-HL1), p-CH3OC6H4 (S- or R-HL2)}. These Schiff bases react with copper(II) acetate under reflux to give green microcrystals of bis[(R or S)-2-((E)-1-(1-(Ar)ethylimino)ethyl)phenolato-κ2N,O]-Λ/Δ-copper(II), {Ar = C6H5 (Λ/Δ-Cu-R- or S-L1), p-CH3OC6H4 (Λ/Δ-Cu-R- or S-L2)} with induction of Λ/Δ-chirality at-metal. The presence of Schiff base ligands in the paramagnetic green microcrystals is confirmed by decomplexation reaction with NaCN via reduction of Cu(II) to Cu(I) in DMSO-d6 solution. Crystallization attempts of the green microcrystalline Schiff-base Cu complexes provide deep-green block-shaped crystals of an about equal admixture of bis[2-oxo-benzophenonato-κ2O,O′]-copper(II), (CuL′2) and bis[2-(imino(phenyl)methyl)phenolato-κ2N,O]copper(II), (CuL′′2) via in situ hydrolysis of the coordinated Schiff base ligands back to 2-hydroxy-benzophenone (HL′) and to 2-(imino(phenyl)methyl)phenol (HL′′), which in-turn bind with the copper(II) ion. Powder X-ray diffraction (PXRD) patterns of R-HL1 and Cu-R-L1 allowed their structure determinations using the program Expo-2014 followed by Rietveld refinement. The Cu structures refined to four-coordinated Λ/Δ-copper(II)-complexes by the two phenolate-oxygen and two imine-nitrogen atoms from two Schiff base ligands in a pseudotetrahedral geometry. DFT optimized structures (at gas-phase) reveal the Δ-Cu-S-L1 or Λ-Cu-R-L1 diastereomer as slightly more stable than the corresponding Λ-Cu-S-L1 or Δ-Cu-R-L1 by ca. 7.60 kcal mol−1, resulting from diastereoselectively induced Λ vs. Δ-chirality at-metal. Electronic circular dichroism (ECD) spectra display mirror-image relationships and comparisons of experimental and simulated ECD spectra by TDDFT suggest an excess of the Δ-Cu-S-L1 or Λ-Cu-R-L1 diastereomer in solution. The cyclic voltammograms demonstrate two one electron charge transfer processes for Cu2+/Cu+ and Cu+/Cu0 couples in acetonitrile, respectively.

Graphical abstract: Pseudotetrahedral copper(ii)-complexes with enantiopure (R or S)-2-(((aryl)ethylimino)ethyl)phenolate Schiff base ligands

Supplementary files

Article information

Article type
Paper
Submitted
23 mai 2021
Accepted
08 jun 2021
First published
08 jun 2021
This article is Open Access
Creative Commons BY-NC license

Dalton Trans., 2021,50, 9236-9249

Pseudotetrahedral copper(II)-complexes with enantiopure (R or S)-2-(((aryl)ethylimino)ethyl)phenolate Schiff base ligands

M. Enamullah, M. Anwar Hossain, M. K. Islam, D. Woschko and C. Janiak, Dalton Trans., 2021, 50, 9236 DOI: 10.1039/D1DT01671G

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