Gas-Phase Interaction of Anions with Polyisobutylenes: Collision-Induced Dissociation Study and Quantum Chemical Modeling

作者：Nagy Lajos; Kuki Akos; Deak Gyorgy; Purgel Mihaly; Vekony Adam; Zsuga Miklos; Keki Sandor^*

来源：Journal of Physical Chemistry B, 2016, 120(34): 9195-9203.

DOI：10.1021/acs.jpcb.6b05655

The gas-phase interaction of anions including fluoride, chloride, bromide, iodide, ethyl sulfate, chlorate, and nitrate with polyisobutylene (Pm) derivatives was studied using collision-induced dissociation (CID). The gas-phase adducts of anions with PIBs ([PIB + anion](-)) were generated from the electrosprayed solution of PIBs in the presence of the corresponding anions. The so-formed adducts subjected to CID showed a loss of anion at different characteristic collision energies, thus allowing the study of the strength of interaction between the anions and nonpolar PIBs having different end groups. The values of characteristic collision energies (the energy needed to obtain 50% fragmentation) obtained by CID experiments correlated linearly with the binding enthalpies between the anion and PIB, as determined by density functional theory calculations. In the case of halide ions, the critical energies for dissociation, :that is, the binding enthalpies for [PIB anion"- adducts, increased in the order of I- < Br- < Cl- Furthermore, it:was found. that the binding enthalpies for the adducts formed with halide ions decreased approximately with the square radius of the halide ion, suggesting that the strength of interaction is mainly determined by the "surface" charge density of the halide-ion. In addition., the characteristic collision energy versus the number of isobutylene units revealed a linear dependence.

• 出版日期2016-9-1