Base-Catalyzed Hydrogen/Deuterium Exchange between Water and Acetonitrile in Anionic Water Clusters

Autor:	Brigitte S. Fox-Beyer, Martin K. Beyer, Vladimir E. Bondybey, Iulia Balteanu, O. Petru Balaj, Chi-Kit Siu
Rok vydání:	2004
Předmět:	chemistry.chemical_compound Deuterium Chemistry Solvation Cluster (physics) Hydrogen–deuterium exchange Water cluster Physical and Theoretical Chemistry Acetonitrile Photochemistry Catalysis Methyl group
Zdroj:	The Journal of Physical Chemistry A. 108:7506-7512
ISSN:	1520-5215 1089-5639
Popis:	An H/D-exchange reaction involving the methyl group of acetonitrile is observed in the small anionic water cluster OH-(CD3CN)(H2O)2. In this cluster, a randomization of H and D atoms takes place, and in subsequent collisions with CD3CN, 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.
Databáze:	OpenAIRE
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