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Gas phase behavior of radical cations of perfluoroalkyl‐1,2,4‐triazines: an experimental and theoretical study
Author(s) -
Giorgi Gianluca,
Piccionello Antonio Palumbo,
Pace Andrea,
Buscemi Silvestre
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.1622
Subject(s) - chemistry , ion , ionic bonding , electron ionization , ring (chemistry) , density functional theory , unpaired electron , fragmentation (computing) , computational chemistry , ionization , thermal decomposition , decomposition , dissociation (chemistry) , mass spectrometry , molecule , organic chemistry , chromatography , computer science , operating system
Electron ionization mass spectrometry and low‐energy collision‐induced decomposition reactions occurring in a tridimensional ion trap, together with density functional theory (DFT) calculations on neutrals, even‐ and odd‐electron cations, have been used to study the gas‐phase ion chemistry of a series of perfluoroalkyl‐1,2,4‐triazines. Loss of oxygen, due to thermal degradation occurring before ionization, likely involving the hydroxylamino group, has been observed. Compounds having a carbonyl group at position 6 of the triazine ring fragment in the source by elimination of NO followed by HF or CO. The decomposition pathways occurring due to CID experiments have shown interesting features depending on the nature and structure of precursor ions. Most of them involve elimination of endocyclic atoms, thereby producing contraction of the original six‐membered ring or formation of acyclic structures. DFT (B3LYP/6‐31G(d,p)) calculations have been used for evaluating structure, stability and properties of neutral and ionic species involved in gas‐phase processes. In particular, it has been calculated that in the molecular ion the unpaired electron is mainly located on the exocyclic nitrogen, while the positive charge is on the C(6) carbon atom. Copyright © 2009 John Wiley & Sons, Ltd.