Related Experiment Video
Updated: Jun 3, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Adamantanes as spherical nanosondes in adducts with a chiral dirhodium complex-discriminating enantiomers and probing
Helmut Duddeck1, Gábor Tóth, Andras Simon
1Institute of Organic Chemistry, Leibniz University Hannover, Schneiderberg 1B, D-30167 Hannover, Germany. duddeck@mbox.oci.uni-hannover.de
Abstract:
Three different kinds of substituted chiral adamantane molecules-adamantanones, dioxolanoadamantanes and dithiolano-adamantanes-were studied in the dirhodium experiment (NMR measurement with 1:1 molar mixtures with Rh((II))(2)[(R)-(+)-MTPA](4) in CDCl(3)). Their different behavior in adduct formation is described, and the possibility of determining enantiomeric purities and absolute configurations is explored. Detailed inspection of one- and two-dimensional NMR experiments allowed for an interpretation of steric and electronic intra-adduct interaction showing that the phenyl groups of Rh* tend to enwrap the bound adamantane ligand so that through-space effects over a range of 6-7 Å away from the binding rhodium atom can be observed. Even slight differences in the relative orientation of phenyl groups can be monitored when comparing diastereomeric adducts via NMR signal dispersion.
Related Concept Videos
Chirality at Nitrogen, Phosphorus, and Sulfur
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
Prochirality
¹H NMR Chemical Shift Equivalence: Enantiotopic and Diastereotopic Protons
In chiral compounds such as 2-butanol, replacing the methylene hydrogens at C3 produces a pair of...
Naming Enantiomers
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution
Racemic Mixtures and the Resolution of Enantiomers
