TY - JOUR
T1 - Characterization of Iron-Sulfur Cubane Clusters by Fast Atom Bombardment Mass Spectrometry
T2 - The Formation of Ionic [FemSn] Clusters through Gas-Phase Unimolecular Reduction Processes and Their Solution Parallels
AU - Lee, Wen Lian
AU - Gage, A.
AU - Huang, Zhi Heng
AU - Chang, Chi K.
AU - Kanatzidis, Mercouri G.
AU - Allison, John
PY - 1992/8/1
Y1 - 1992/8/1
N2 - 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.
AB - 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.
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U2 - 10.1021/ja00044a027
DO - 10.1021/ja00044a027
M3 - Article
AN - SCOPUS:0011954722
SN - 0002-7863
VL - 114
SP - 7132
EP - 7141
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 18
ER -