Characterization of Iron-Sulfur Cubane Clusters by Fast Atom Bombardment Mass Spectrometry: The Formation of Ionic [FemSn] Clusters through Gas-Phase Unimolecular Reduction Processes and Their Solution Parallels

Wen Lian Lee, Douglas A. Gage, Zhi Heng Huang, Chi K. Chang, Mercouri G. Kanatzidis, John Allison

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Abstract

Fast atom bombardment mass spectrometry (FAB-MS) has been used to analyze a series of iron-sulfur clusters (A)2Fe4S4X4, where A = R4N or Ph4P and X = Cl, Br, SEt, SPh. A cluster with mixed Cl, SPh ligands was also studied. The usefulness of the FAB technique in characterizing these and related biologically-relevant complexes is evaluated. The best FAB-MS results for these clusters were obtained with 3-nitrobenzyl alcohol (NBA) and 2-nitrophenyl octyl ether (NPOE) as matrices. The most unique feature of the negative ion FAB mass spectra is the identification of the intact ionic core [Fe4S4X4]-, preformed anions [(A)Fe4S4X4]-, and a series of cluster fragment ions. A mechanism is proposed to explain the formation of small [FemSn] clusters through unimolecular reduction processes that involve only +2 and +3 oxidation states for the Fe atoms. This work demonstrates that FAB-MS can be employed as a valid method for rapid molecular weight determination as well as structural elucidation of [Fe4S4] cluster-containing complexes.

Original languageEnglish
Pages (from-to)7132-7141
Number of pages10
JournalJournal of the American Chemical Society
Volume114
Issue number18
DOIs
Publication statusPublished - Aug 1 1992

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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