Encapsulation of protonated diamines in a water-soluble, chiral, supramolecular assembly allows for measurement of hydrogen-bond breaking followed by nitrogen inversion/rotation.

Abstract

Amine nitrogen inversion, difficult to observe in aqueous solution, is followed in a chiral, supramolecular host molecule with purely rotational T-symmetry that reduces the local symmetry of encapsulated monoprotonated diamines and enables the observation and quantification of Delta G (++) for the combined hydrogen-bond breaking and nitrogen inversion/rotation (NIR) process. Free energies of activation for the combined hydrogen-bond breaking and NIR process inside of the chiral assembly were determined by the NMR coalescence method. Activation parameters for ejection of the protonated amines from the assembly confirm that the NIR process responsible for the coalescence behavior occurs inside of the assembly rather than by a guest ejection/NIR/re-encapsulation mechanism. For one of the diamines, N, N, N', N'-tetramethylethylenediamine, the relative energy barriers for the hydrogen-bond breaking and NIR process were calculated at the G3(MP2)//B3LYP/6-31++G(d,p) level of theory, and these agreed well with the experimental data.

DOI: 10.1021/ja076691h

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Cite this paper

@article{Pluth2008EncapsulationOP, title={Encapsulation of protonated diamines in a water-soluble, chiral, supramolecular assembly allows for measurement of hydrogen-bond breaking followed by nitrogen inversion/rotation.}, author={Michael D Pluth and Robert G. Bergman and Kenneth N Raymond}, journal={Journal of the American Chemical Society}, year={2008}, volume={130 20}, pages={6362-6} }