title: Mass spectrometry study and infrared spectroscopy of the complex between camphor and the two enantiomers of protonated alanine: the role of higher-energy conformers in the enantioselectivity of the dissociation rate constants.
abstract: The properties of the protonated complexes built from S camphor and R or S alanine were studied in a Paul ion trap at room temperature by collision-induced dissociation (CID) and infrared multiple-photon dissociation spectroscopy (IRMPD), as well as molecular dynamics and ab initio calculations. While the two diastereomer complexes display very similar vibrational spectra in the fingerprint region, in line with similar structures, and almost identical calculated binding energies, their collision-induced dissociation rates are different. Comparison of the IRMPD results to computed spectra shows that the SS and SR complexes both contain protonated alanine strongly hydrogen-bonded to the keto group of camphor. The floppiness of this structure around the NH⁺...O=C hydrogen bond results in a complex potential energy surface showing multiple minima. Calculating the dissociation rate constant within the frame of the transition state theory shows that the fragmentation rate larger for the heterochiral SR complex than the homochiral SS complex can be explained in terms of two almost isoenergetic low-energy conformers in the latter that are not present for the former.
authors.affiliation: CNRS, Institut des Sciences Moléculaires d'Orsay, UMR8214, Orsay, France.
authors.forename: Ananya
authors.initials: A
authors.lastname: Sen
authors.forename: Katia
authors.initials: K
authors.lastname: Le Barbu-Debus
authors.forename: Debora
authors.initials: D
authors.lastname: Scuderi
authors.forename: Anne
authors.initials: A
authors.lastname: Zehnacker-Rentien
mesh_terms: D000409:Alanine / Q000737:chemistry*; D002164:Camphor / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D013058:Mass Spectrometry; D008958:Models, Molecular; D011522:Protons; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism
chemical_list: D056831:Coordination Complexes; D011522:Protons; D002164:Camphor; D000409:Alanine
keywords: IRMPD; collision-induced dissociation; entropic effects; homochiral preference; mass spectrometry; vibrational spectroscopy