Interpretation of alkyl diselenide and selenosulfenate mass spectra

Juris Meija, Thomas L. Beck, Joseph A. Caruso

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

The mass spectral fragmentation of aliphatic diselenides and selenosulfenates is analyzed to gain a better understanding of the behavior of these species. The main fragmentation pathways of these species include the fragmentation along the Se-C bond, fragmentation along the Se-Se or Se-S bonds and intra-molecular rearrangements. In general, negative ionization favors the fragmentation along the Se-Se or Se-S bonds while positive ionization leads to stable molecular ions. Density functional theory calculations of bond dissociation energies and molecular orbital analysis was undertaken to explain the observed trends in molecular fragmentation. Besides the analysis of molecular fragmentation, a phenomenon of molecular association in negative electron impact and positive chemical ionization conditions was observed and investigated using a high resolution time-of-flight mass spectrometer. Molecular association that occurs during the ionization of species includes the formation of symmetrical diselenides from asymmetrical selenosulfenates and formation of alkylseleno adducts from the corresponding diselenides. For species which is hard to resolve by mass analysis, such as isobars of CHSe, CH2Se, and CH3Se, the isotope pattern superimposition procedure was applied to define the overlapping clusters.

Original languageEnglish
Pages (from-to)1325-1332
Number of pages8
JournalJournal of the American Society for Mass Spectrometry
Volume15
Issue number9
DOIs
StatePublished - Sep 2004
Externally publishedYes

Funding

The authors thank the Mass Spectrometry Facility at the University of Cincinnati for the use of GC-TOF-MS. Computing time was generously provided by the Molecular Modeling Services at the University of Cincinnati. JM thanks Anping Liu for his generous assistance in technical aspects of computational processing. This research was partially supported by NIEHS-SBRP grant ES04908 (JAC) and NSF grant CHE-0112322 (TLB).

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