Base-catalyzed hydrogen/deuterium exchange between water and acetonitrile in anionic water clusters

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

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Author(s)

  • O. Petru Balaj
  • Iulia Balteanu
  • Brigitte S. Fox-Beyer
  • Martin K. Beyer
  • Vladimir E. Bondybey

Detail(s)

Original languageEnglish
Pages (from-to)7506-7512
Journal / PublicationJournal of Physical Chemistry A
Volume108
Issue number37
Publication statusPublished - 16 Sep 2004
Externally publishedYes

Abstract

An H/D-exchange reaction involving the methyl group of acetonitrile is observed in the small anionic water cluster OH-(CD 3CN)(H2O)2. In this cluster, a randomization of H and D atoms takes place, and in subsequent collisions with CD 3CN, the potentially partially deuterated acetonitrile is replaced by the fully deuterated species. In sequential collisions, fully deuterated clusters OD-(CD3CN)(D2O)2 are obtained as final products. The H/D-exchange does not occur in OH -(CD3CN)(H2O)3 or larger clusters. Density functional calculations show that in these larger species, the OH - no longer directly attacks the methyl group, and the barriers for H/D-exchange become higher than those for ligand loss reaction channels. This is a very subtle influence of solvation on an H/D-exchange reaction in the gas phase, where a relatively acidic methyl group encounters a strongly basic reaction partner.

Citation Format(s)

Base-catalyzed hydrogen/deuterium exchange between water and acetonitrile in anionic water clusters. / Balaj, O. Petru; Siu, Chi-Kit; Balteanu, Iulia et al.

In: Journal of Physical Chemistry A, Vol. 108, No. 37, 16.09.2004, p. 7506-7512.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review