Adamantanes as spherical nanosondes in adducts with a chiral dirhodium complex - discriminating enantiomers and probing spatial proximities

作者：Duddeck Helmut^*; Toth Gabor; Simon Andras; Gomez Edison Diaz; Mattiza Jens T

来源：Magnetic Resonance in Chemistry, 2011, 49(6): 328-342.

DOI：10.1002/mrc.2751

• dirhodium complexes
• adamantanones
• dioxolanoadamantanes
• dithiolanoadamantanes
• (1)H and (13)C NMR
• anisotropy effects
• NOE
• spatial orientation
• chiral differentiation
• absolute configuration

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(2)((II))[(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 angstrom 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.

• 出版日期2011-6