Conformational analysis. Part 25. The evaluation of molecular geometries by the lanthanide induced shift (LIS) technique

Abstract

A refined lanthanide induced shift (LIS) technique, using Yb(fod)₃ to obtaian the paramagnetic induced shifts of all the spin 1/2 nuclei in the molecule, together with complexation shifts obtained by the use of Lu(fod)₃ has been used to test the accuracy of molecular geometries obtained by various theoretical methods, including molecular mechanics and ab initio calculations with the RHF/6-31G* basis set.

The technique has been applied to a series of aromatic aldehydes, ketones and esters. The relative strengths and weaknesses of the calculated geometries are clearly illustrated by this technique. Although the ab initio geometries generally gave better agreement with the observed LIS than geometries generated by molecular modelling programs, as expected, this was not always the case, particularly for the 2,6-difluoro compounds.

The LIS were also used to differentiate between two experimental geometries for 2,6-dimethylacetophenone. Thus the method outlined here is general and can in principle be applied to any derived molecular geometry.