Solid-state to solution helicity inversion of pseudotetrahedral chiral copper(ii) complexes with 2,4-dihalo-salicylaldiminate ligands

Dalton Transactions : an International Journal of Inorganic Chemistry
Nazanin KordestaniMohammed Enamullah

Abstract

The enantiopure Schiff bases (R or S)-N-1-(phenyl)ethyl-2,4-X1,X2-salicylaldimine (X1, X2 = Cl, Br, I) coordinate to copper(ii) and provide pseudotetrahedral bis[(S or R)-N-1-(phenyl)ethyl-(2,4-X1,X2-salicylaldiminato-κ2N,O)]-Δ/Λ-Cu(ii) (Λ/Δ-Cu-R or Δ/Λ-Cu-S). An induced Λ and Δ-chirality at-metal centre has been launched along the C2-axis of the molecule. Steric constraints brought by halogen substituents on the coordinating salicylal ring provide diastereoselectively Λ-Cu-R or Δ-Cu-S as major and Δ-Cu-R or Λ-Cu-S as minor diastereomers at solid-state, as evidenced by X-ray crystal structures and PXRD analyses. These results reveal inversion of induced chirality at-metal in comparison to the similar complexes without halogen substituents on the salicylal ring. Electronic circular dichroism (ECD) spectra show mirror-image relationships, confirming enantiomeric excess of the R or S-ligated complexes in solution. Comparisons of experimental and simulated ECD spectra suggest diastereomeric excess of Δ-Cu-R or Λ-Cu-S in solution which correspond to an inversion from the found solid-state Λ-Cu-R or Δ-Cu-S as major diastereomers. In addition, the optimized gas-phase structures also reveal Δ-Cu-R or Λ-Cu-S as slightly more stable than...Continue Reading

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Citations

Jun 16, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Mohammed EnamullahChristoph Janiak
Jan 20, 2022·Dalton Transactions : an International Journal of Inorganic Chemistry·Hadi Amiri RudbariMohammed Enamullah

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Methods Mentioned

BETA
X-ray
circular dichroism
differential scanning calorimetry

Software Mentioned

Bruker APEX3
XL
SHELXTL
EvalCCD
XT
CrystalExplorer
Bruker
ADDSYM
SpecDis
PLATON

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