Ammonium adducts of trimethylsilyl-terminated poly(dimethylsiloxane) (CH(3)-PDMS) produced by electrospray ionization were submitted to collision induced dissociation and revealed a particular MS/MS behavior: the same three main product ions at m/z 221, 295, and 369 were always generated in very similar relative abundances regardless of the size of the precursor ion. Combining accurate mass measurements and ab initio calculation allowed very stable cyclic geometries to be obtained for these ionic species. Dissociation mechanisms were proposed to account for the three targeted ions to be readily generated in a two-step or a three-step reaction from any CH(3)-PDMS ammonium adducts. A second set of three product ions was also observed with low abundance at m/z 207, 281, and 355, which were shown in MS(3) experiments to be formed in secondary reactions. An alternative dissociation process was shown to consist of a concerted elimination of ammonia and methane and the need for a methyl of an end-group to be involved in the released methane molecule would account for this reaction to mainly proceed from the smallest precursor ions.
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