Fast atom bombardment-mass spectrometry cluster ions

In fast-atom bombardment mass spectrometry (FAB) primary neutral atoms of energies 3—10 keV are used to sputter clusters and molecular ions from the sample. 

Older soft ionization methods that are related to MALDl—such as fast atom bombardment (FAB), hquid secondary ion mass spectrometry (LSIMS), or field desorption (FD)— in principle have potential for the generation of intact gas-phase ions from noncovalent complexes. In particular, the extensive clustering often found in FAB-MS, which is generally thought of as a nuisance, can be viewed as evidence for this. However, the limitation of these methods lies in their inabiUty to ionize very large molecules. It is generally very difficult or impossible to obtain useful mass spectra from compounds with molecular weights above a few thousand daltons. For this reason, FAB-MS, LSIMS, and FD-MS only play a very minor role in this field. 

Mass spectral analysis of quaternary ammonium compounds can be achieved by fast-atom bombardment (fab) ms (189,190). This technique rehes on bombarding a solution of the molecule, usually in glycerol [56-81-5] or y -nitroben2yl alcohol [619-25-0], with argon and detecting the parent cation plus a proton (MH ). A more recent technique has been reported (191), in which information on the stmcture of the quaternary compounds is obtained indirectly through cluster-ion formation detected via Hquid secondary ion mass spectrometry (Isims) experiments. 

Example Cesium iodide is frequently used for mass calibration in fast atom bombardment (FAB) mass spectrometry (Chap. 9) because it yields cluster ions of the general formula [Cs(CsI)n] in positive-ion and [I(CsI)J in negative-ion mode. For the [Cs(CsI)io] cluster ion, m/z 2730.9 is calculated instead of the correct value m/z 2731.00405 by using only one decimal place instead of the exact values Mi33Cs = 132.905447 and M1271 = 126.904468. T e error of 0.104 u is acceptable for LR work, but definitely not acceptable if accurate mass measurements have to be performed. 

More recently, studies concerning cluster ion formation from solid or deeply cooled liquid alcohols [120-122] have gained new interest. [123,124] Low-temperature fast atom bombardment (LT-FAB) of frozen aqueous solutions of metal salts provides a source of abundant hydrated metal ions. [125-127] Organic molecules can also be detected from their frozen solutions. [128] Such LT-FAB applications are particularly interesting when enabling the detection of species that would otherwise not be accessible by mass spectrometry, because they are either extremely air- and/or water-sensitive [129,130] as the phosphaoxetane intermediate of the Wittig reaction [131] or insoluble in standard FAB matrices. [106,132]... 

Plavsic, Srzic and Klasinc performed a detailed electron impact mass spectrometric investigation of alkyllithium compounds . They have concluded that MeLi, /-PrLi, 5-BuLi and r-BuLi consist of tetrameric clusters only, while n-PrLi, n-BuLi and i-BuLi form mixtures of tetramers and hexamers, in the gas phase. Fast atom bombardment (FAB) mass spectrometry was used by Abdul-Sada, Greenway and Seddon to show that the extent of aggregation of f-BuLi is tetrameric while n-BuLi is hexameric (Table 1). Nevertheless, for both alkyllithium compounds the ion corresponding to (RLi)Li+ is the most abundant in the spectrum, as also shown in other studies of alkyllithium vapor. 

A study comparing plasma desorption (PD) and fast atom bombardment (FAB) mass spectrometry to characterize clusters of this type found that the isocyanide-capped clusters 30 showed strong molecular ion peaks by both methods. PD and FAB were also used to identify the molecular ions of dimers of trimers, ... 

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