Reaction diastereoselectivity of chiral aminoalcohols/[Co(II)NO3]+ complexes in evaporating ESI nanodroplets: new insights from a joint experimental and computational investigation.

The nature of the ionic species, formed by electrospray ionization (ESI) of Co(NO3)2/CH3OH solutions with a pair of aminoalcohols W and Y, has been investigated by mass spectrometric and computational methods. Collision induced dissociation (CID) of ions, formally corresponding to the [WYCoNO3]+ structures, yields fragmentation patterns which reflect not only the expected [WYCoNO3]+ connectivity but also that of other isomeric structures. Formation of these latter species is observed only in the presence of a tertiary aminoalcohol, like N-methylpseudoephedrine. The CID patterns are found to be strongly dependent on the chemical form (whether the free aminoalcohol or its hydrochloride), the configuration, and the relative concentration of the W and Y aminoalcohols. This variability parallels the results of classical MD (molecular dynamics) simulations of the [WYCoNO3]+ adducts which show a drastic alteration of the mechanical-dynamical features of the adducts by simply changing the charge state of W and/or Y, their absolute configuration, or by removing the solvent. The present experimental and computational study confirms the observation of fast stereoselective reactions in ESI nanodroplets before their evaporation and warns against any automatic correlation between the ESI spectrum of an analyte and its structure in solution.