Gas-phase hydrogen/deuterium exchange reactions on hydrogen-bonded ions yield quite detailed information on mechanistic and structural aspects of isolated supramolecules. It has been utilized to provide evidence for the intramolecular mobility of crown ethers within oligolysin/crown-6 and POPAM dendrimer/crown-6 complexes and thus highlights the surprisingly pronounced dynamics within such complexes.
Furthermore, a concerted H/D-exchange mechanism operating in dimeric resorcinarene capsules could be detected which resembles a one-dimensional variant of the well-known Grotthus mechanism for proton transport in water.
These H/D-exhcange experiments finally resulted in the observation that large crowns (e.g. crown-8 and beyond) catalytically drive the ammonia elimination reaction of primary amines by simultaneously enhancing the leaving group capability of the ammonia molecule and offering a base for the proton at C(2).
Mercator projection of the hydrogen bonding seam of a dimeric resorcinarene capsule and concerted H/D-exchange reaction with methanol-OD
Multivalency in the Gas Phase: H/D-Exchange Reactions Unravel the Dynamic 'Rock 'n Roll' Motion in Dendrimer-Dendrimer Complexes
Z. Qi, C. Schlaich, C.A. Schalley
Chem. Eur. J. 2013, 19, 14867-14875
Gas-phase organocatalysis with crown ethers
H.D.F. Winkler, E.V. Dzyuba, A. Springer, L. Losensky, C.A. Schalley
Chem. Sci. 2012, 3, 1111-1120
Gas-phase H/D-exchange reactions on resorcinarene and pyrogallarene capsules: Proton transport through a one-dimensional Grotthuss mechanism
H.D.F. Winkler, E.V. Dzyuba, J.A.W. Sklorz, N.K. Beyeh, K. Rissanen, C.A. Schalley
Chem. Sci. 2011, 2, 615-624
Gas-phase H/D-exchange experiments in supramolecular chemistry
H.D.F. Winkler, E.V. Dzyuba, C.A. Schalley
New J. Chem. 2011, 35, 529-541
Dynamic Motion in Crown Ether-Dendrimer Complexes: A "Spacewalk" on the Molecular Scale
H.D.F. Winkler, D.P. Weimann, A. Springer, C.A. Schalley
Angew. Chem. 2009, 121, 7382-7386; Angew. Chem. Int. Ed. 2009, 48, 7246-7250
Highly dynamic motion of crown ethers along oligolysine peptide chains
D.P. Weimann, H.D.F. Winkler, J.A. Falenski, B. Koksch, C.A. Schalley
Nature Chem. 2009, 1 573-577