Abstract
The principal collision-induced fragmentations of simple protonated ketones, aldehydes, ethers, amines, sulphides, alcohols, acids, nitriles and halides are discussed. These protonated molecules decompose mainly by loss of alkane, alkene and RX (R = alkyl, H; X = OH, SH, NH 2, Br, I). Substantial radical losses are only observed for small protonated molecules. Deuterium-labelling demonstrates that the XH bond is particularly strong. The fragmentation of (MH) + ions is compared with that of the corresponding (M) +− ions. The spectra of the (M) +− ions are dominated by direct bond cleavages, in particular α-cleavages, as a result of both the stability of the ionic fragment and the loose transition state. In (MH) + ions direct bond cleavages lead to energetically less favourable products. Thus rearrangement reactions play a more important role in the decomposition of these ions. (MH) + ions are more stable relative to fragmentation than (M) +− ions.
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