Intracluster proton transfer in aniline–amine complex ions

Abstract

The intracluster proton transfer in aniline-amine complex ions is investigated by infrared photodissociation spectroscopy and density functional theory calculations. The p roton acceptors include ammonia, methylamine, dimethylamine and trimethylamine in asce nding order of proton affinity. The spectra of (aniline-ammonia) + and (aniline-methylami ne) + demonstrate the persistence of the aniline ion unit in the complexes. For (aniline-di methylamine) + and (aniline-trimethylamine) + , the spectra imply the transformation to the a nilino radical (C 6 H 5 NH) unit, suggesting the occurrence of the proton transfer.

Dihydrogen Bond Intermediated Alcoholysis of Dimethylamine–Borane in Nonaqueous Media

“…1.7–6.5 kcal/mol for PNP and 0.7–6.4 kcal/mol for HFIP, lower than those for simple substitution, while the products are stabilized by 0.8–10.6 kcal/mol (Figure ). The Me 2 NH·HFIP complex easily undergoes proton transfer yielding dimethylammonium-cation [Me 2 NH 2 ] + , while BH 3 transforms gradually into [B­(OR) 4 ] − by the reaction with the excess alcohol. Protonation of neutral BH 3 ·Solv has higher barrier than the B–N bond dissociation ( TS BH of proton transfer from HFIP to BH 3 ·THF has activation energy Δ G ‡ THF = 37.2 kcal/mol).…”

Intermolecular proton-transfer in acetic acid clusters induced by vacuum-ultraviolet photoionization

“…4,17,20,[60][61][62] Correlations of the proton-transfer reaction with the proton affinity in the microsolvated phenol and aniline cations have been illustrated by electronic and vibrational spectroscopies. [17][18][19][20] Generation of protonated species with the matrix-assisted laser desorption/ ionization technique has also been examined with relationship between proton affinities of samples and acidities of matrix molecules. 4,61 For protic molecules, the formation of the intracluster proton-transferred structures in ͑NH 3 ͒ n + , n =2-4, ͑CH 3 OH͒ n + , n=2, 3, and ͑H 2 O͒ 2 + -Ar n , n=1, 2 has experimentally been demonstrated by IR predissociation spectroscopy.…”

“…[13][14][15][16] Formation of the proton-transferred structures have also been concluded for solvated phenol and aniline cluster cations. [17][18][19][20] An important problem related to intermolecular protontransfer in the gas phase is generation of protonated species in ionization processes. 3,[7][8][9][10][11][12][21][22][23] For protic molecules such as water, alcohol, ammonia, and aliphatic acids, protonated species are dominant products with typical ionization techniques such as discharge, electron impact, and multiphoton ionization.…”

Fermi resonance interaction in hetero-dimer and trimer ions containing aniline+

“…They discussed t he detailed structures of aniline + -Ar n with the aid of ab initio calculations. Our group has investigated intermolecular interactions, geometric structures and intermolecular proton tra nsfers of aniline + cluster ions [5][6][7][8]. In the 2600-3600 cm -1 region of the infrared spectr a of certain aniline + cluster ions, an extra band emerges in addition to two strong NH stret ching bands.…”