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Mass Spectrometric Investigation of Noncovalent Complexation between a Tetratosylated Resorcarene and Alkyl Ammonium Ions

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Abstract

Noncovalent complexation between tetratosylated tetraethyl resorcarene (1) and primary, secondary, and tertiary alkyl ammonium ions (mMe, dMe, tMe, mEt, dEt, tEt, dBu, and dHex) was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. Interactions of the noncovalent complexes were investigated by means of competition experiments, collision-induced dissociation (CID) experiments, ion–molecule reactions with tripropylamine and gas phase H/D-exchange reactions with deuteroammonia. Gas phase ion–molecule reactions gave especially valuable information about the structure and properties of the complexes. Resorcarene 1 formed relatively stable 1:1 complexes with all aliphatic alkyl ammonium ions. Steric properties of the alkyl ammonium ions and proton affinities of the conjugate amines noticeably affected the complexation properties, indicating the importance of hydrogen bonding in these complexes. According to the competition experiments, the thermodynamically most stable host–guest complexes were formed with alkyl ammonium ions that were most substituted and had the longest alkyl chains. In CID experiments, release of an intact free guest ion or dissociation of the host was observed to depend on the proton affinity of the amine and the strength of the hydrogen bond that was formed. In ion–molecule reactions with tripropylamine, a guest exchange reaction occurred with all alkyl ammonium ion complexes with reaction rates mostly dependent on the steric properties of the original guest ion. In H/D-exchange reactions the N-H hydrogen atoms of the guest ion were exchanged with deuterium, whereas the resorcinol hydrogen atoms remained unchanged.

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