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Issue 35, 2012
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Vibrational circular dichroism spectroscopy of two chiral binaphthyl diphosphine ligands and their palladium complexes in solution

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Abstract

BINAP (2,2′-diphenylphosphino-1,1′-binaphthyl) is a unique binaphthyl diphosphine ligand with axial chirality. The palladium complexes of BINAP and of its derivative TOLBINAP have found extensive applications in the field of asymmetric syntheses. The conformational changes in the BINAP and TOLBINAP ligands before and after coordination with palladium have been investigated using density functional theory, vibrational absorbance (VA) and vibrational circular dichroism (VCD) spectroscopy. VA and VCD spectra of these two chiral ligands and their corresponding palladium complexes have been recorded in CDCl3 solution. Extensive conformational searches have been carried out for both the ligands and the associated palladium complexes. Coordination with palladium has been found to introduce structural rigidity to the ligands. The calculated VA and VCD spectra of the ligands and complexes in the gas phase show substantial differences to the experimental data. Incorporation of the implicit polarisable continuum solvation model has provided much better agreement between theory and experiment, especially for the complexes, allowing clear identification of the species and conformations. This and the high specificity of VCD spectral signatures to chirality and to conformations suggest the potential applications of VCD spectroscopy for following these important catalytic species in solution reactions directly.

Graphical abstract: Vibrational circular dichroism spectroscopy of two chiral binaphthyl diphosphine ligands and their palladium complexes in solution

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Supplementary files

Article information


Submitted
01 Jun 2012
Accepted
10 Jul 2012
First published
16 Jul 2012

Dalton Trans., 2012,41, 10817-10824
Article type
Paper

Vibrational circular dichroism spectroscopy of two chiral binaphthyl diphosphine ligands and their palladium complexes in solution

Z. Dezhahang, C. Merten, M. R. Poopari and Y. Xu, Dalton Trans., 2012, 41, 10817
DOI: 10.1039/C2DT31184D

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