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Collision‐induced loss of AgH from Ag + adducts of alkylamines, aminocarboxylic acids and alkyl benzyl ethers leads exclusively to thermodynamically favored product ions
Author(s) -
Schäfer Mathias,
Dreiocker Frank,
Budzikiewicz Herbert
Publication year - 2009
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1507
Subject(s) - chemistry , methylene , hydride , alkyl , ether , deuterium , medicinal chemistry , dissociation (chemistry) , ion , adduct , isotopic labeling , aryl , kinetic isotope effect , photochemistry , organic chemistry , hydrogen , physics , quantum mechanics
The loss of AgH from [M + Ag] + precursor ions of tertiary amines, aminocarboxylic acids and aryl alkyl ethers is examined by deuterium labeling combined with collision activation (CA) dissociation experiments. It was possible to demonstrate that the AgH loss process is highly selective toward the hydride abstraction. For tertiary amines and aminocarboxylic acids, hydrogen originates from the α‐methylene group carrying the nitrogen function (formation of an immonium ion). In all cases examined, the most stable, i.e. the thermodynamically favored product ion is formed. In the AgH loss process, a large isotope effect operates discriminating against the loss of D. The [M + Ag] + ion of benzyl methyl ether loses a hydride ion exclusively from the benzylic methylene group supporting the experimental finding that the AgH loss reaction selectively cleaves the weakest CH bond available. Copyright © 2008 John Wiley & Sons, Ltd.