Investigation of unexpected silane ions caused by gas‐phase reactions in Orbitrap gas chromatography–mass spectrometry

Abstract

RationaleThe mass spectra of compounds containing dimethyl (phenyl)silyl group (‐SiMe2Ph) sometimes exhibit unusual ion peaks when measured using Orbitrap gas chromatography–mass spectrometry (GC–MS). This would complicate the mass spectra and may limit the matching of spectral data with preexisting resources for compound annotation. These peaks were identified as products from reactions with residual water.MethodsA series of dimethyl (phenyl)silyl compounds were dissolved in methanol and investigated using Orbitrap GC–MS. Certain ions reacted with residual water in the C‐trap. The reaction was confirmed using accurate mass and elemental composition analysis via MS studies, and the active center of the reaction was determined using density functional theory (DFT) calculations.ResultsTwo types of gas‐phase reactions between gaseous water and cations from a series of silanes were identified. DFT calculations indicate that silicon (Si) acts as the active center for these gas‐phase water reactions. Compounds with multiple Si atoms generate a larger number of additional ions, which would complicate the mass spectra. The mass spectra of vinylsilanes and alkylsilanes with ‐SiMe2Ph indicate that the conjugated group linked to ‐SiMe2Ph can affect the water adduction process.ConclusionsSilane ions could react with residual water in the C‐trap of an Orbitrap mass spectrometer. The mass spectra of these compounds may exhibit unexplained peaks arising from gas‐phase reactions. Although these reactions may decrease spectral matching scores for compound annotation, they offer opportunities for systematic investigations into the mechanistic and kinetic aspects of high‐energy ion reactivity.