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Kanawati, B. ; Wanczek, K.-P.*

Phosphoranide production and decomposition in the gas phase.

Int. J. Mass Spectrom. 362, 18-23 (2014)
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After characterizing the negative ion chemistry of tris(trifluoromethyl) phosphine in a previous work, new insights about the interpretation of the MS/MS mass spectrum of the phosphide anion (CF3)2P- m/z 169 could be revealed and are described in this current work. The phosphide (CF3)2P- anion, m/z 169, was accelerated in a cloud of (CF3)3P neutrals and new product ions could be detected which do not belong to fragmentation channels. Instead, high mass anions m/z 207 and m/z 257 are found, and the reaction mechanism could be revealed by density functional theory (DFT) calculations at B3LYP/6-311 + G(3df)//B3LYP/6-31 + G(2d) level of theory. The formation of the phosphoranide (CF3)3PF- m/z 257 is the result of a fluoride anion transfer from the accelerated phosphide anion (CF3) 2P- m/z 169 to the (CF3)3P neutral m = 238. Decomposition of the newly formed phosphoranide (CF3) 3PF- m/z 257 leads to the formation of smaller phosphoranides (CF3)2PF2 - m/z 207 and CF3PF3 - m/z 157 as a result of successive CF2 eliminations. A new rearrangement in the formed phosphoranide (CF3)2PF2 - could be revealed, whereby a CC bond formation can take place and the product anion C 2F5 - m/z 119 could be experimentally obtained.
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Publikationstyp Artikel: Journalartikel
Dokumenttyp Wissenschaftlicher Artikel
Schlagwörter Energy Barrier ; Ft-icr-ms ; Reaction Mechanism ; Rearrangement; Mass-spectrometric Characterization; Optimizing Large Molecules; Density-functional Theory; Geometry Optimization; Iterative Subspace; Improved Algorithm; Chemical-reactions; Triple Quadrupole; Organic-compounds; Direct Inversion
ISSN (print) / ISBN 1387-3806
e-ISSN 1873-2798
Zeitschrift International Journal of Mass Spectrometry
Quellenangaben Band: 362, Heft: 1, Seiten: 18-23 Artikelnummer: , Supplement: ,
Verlag Elsevier
Verlagsort Amsterdam
Begutachtungsstatus