ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
[Mo3S(S2)3(dtc)3]I, [Mo3S(SeS)3(dtc)3](dtc), and [Mo3Se(Se2)3(dtc)3](dtc) (dtc = N,N-diethyldithiocarbamate) were investigated by liquid SIMS-FTMS. The fragmentation pathways were essentially the same for the three compounds and can be explained by two types of fragmentation processes: stepwise abstraction of S/Se atoms as exemplified by the series [Mo3Xz(dtc)3]+ (4 ≤ z ≤ 7, X = S, Se), and ligand dissociation, as indicated by the generation of [Mo3Xz(dtc)2]+ (5 ≤ z ≤ 7, X = S, Se). The exclusive elimination of the Se-atoms from [Mo3S(Sax-Seeq)3(dtc)3]+ confirmed the inequivalent reactivity of the bridging atoms in axial and equatorial position as observed in previous studies. Collision-induced decomposition (CID) of [Mo3S7(dtc)3]+ (1), [Mo3S6(dtc)3]+ (2), [Mo3S(Sax-Seeq)3(dtc)3]+ (3), and [Mo3Se7(dtc)3]+ (4) revealed distinctly different fragmentation reactions for the SIMS and CID mode. CID of 1, 3, and 4 resulted in a two-step reaction with the exclusive elimination of diatomic molecules XY (X,Y = S/Se). In the case of 3, the selective elimination of Se2 indicated the abstraction of two Se-atoms located in equatorial positions of two different bridging groups. This result is discussed in terms of mechanisms, based on labile M—Xeq and inert M—Xax bonds with an intramolecular formation of a X4 fragment prior to the elimination of X2.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19920750521
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