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Metal‐assisted regioselectivity in nucleophilic substitutions: a study by Raman spectroscopy and density functional theory calculations
Author(s) -
Defant Andrea,
Rossi Barbara,
Viliani Gabriele,
Guella Graziano,
Mancini Ines
Publication year - 2010
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.2631
Subject(s) - density functional theory , raman spectroscopy , chemistry , regioselectivity , nucleophile , substituent , molecule , metal , piperidine , computational chemistry , denticity , nucleophilic substitution , stereochemistry , medicinal chemistry , organic chemistry , physics , optics , catalysis
Abstract A series of complexes (Fe II , Cu II and Ni II ) of the N,O bidentate ligand 6,7‐dichloroquinoline‐5,8‐dione in water was investigated by using Raman spectroscopy, and the experimental peaks were assigned with the help of computed spectra by density functional theory (DFT) calculations. A strong shift to lower wavenumbers was observed for the vibration of the CO group involved in chelation, depending on the type of metal ion. When each complex was used in the substitution reaction by the nucleophilic reagent piperidine, two products having the same molecular composition but showing the substituent in different regions of the molecule were obtained, and moreover their regioselective formation was in agreement with the size of the Raman shifts previously observed for the complexes. This example confirms the potential of the approach involving Raman spectroscopy combined with DFT calculations in the characterization of metal complexes as key intermediates in organic reactions, with the possibility of predicting the metal system capable to achieve the highest selectivity. Copyright © 2010 John Wiley & Sons, Ltd.