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Collision‐Induced Decomposition (CID) of Triangular [Mo 3 S 7‐x Se x ] 4+ Complexes ( x = 0,3,7). A liquid SIMS and FTMS/MS study of [Mo 3 S 7‐x Se x (Et 2 NCS 2 ) 3 ] +
Author(s) -
Hegetschweiler Kaspar,
Caravatti Pablo,
Fedin Vladimir P.,
Sokolov Maxim N.
Publication year - 1992
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19920750521
Subject(s) - chemistry , dissociation (chemistry) , fragmentation (computing) , crystallography , molecule , collision induced dissociation , stereochemistry , analytical chemistry (journal) , mass spectrometry , tandem mass spectrometry , organic chemistry , chromatography , computer science , operating system
[Mo 3 S(S 2 ) 3 (dtc) 3 ]I, [Mo 3 S(SeS) 3 (dtc) 3 ](dtc), and [Mo 3 Se(Se 2 ) 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 [Mo 3 X z (dtc) 3 ] + (4 ⩽ z ⩽ 7, X = S, Se), and ligand dissociation, as indicated by the generation of [Mo 3 X z (dtc) 2 ] + (5 ⩽ z ⩽ 7, X = S, Se). The exclusive elimination of the Se‐atoms from [Mo 3 S(S ax ‐Se eq ) 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 [Mo 3 S 7 (dtc) 3 ] + ( 1 ), [Mo 3 S 6 (dtc) 3 ] + ( 2 ), [Mo 3 S(S ax –Se eq ) 3 (dtc) 3 ] + ( 3 ), and [Mo 3 Se 7 (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 Se 2 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 MX eq and inert MX ax bonds with an intramolecular formation of a X 4 fragment prior to the elimination of X 2 .