IR Spectrum and Structure of Protonated Monosilanol: Dative Bonding between Water and the Silylium Ion

Abstract We report the spectroscopic characterization of protonated monosilanol (SiH 3 OH 2 + ) isolated in the gas phase, thus providing the first experimental determination of the structure and bonding of a member of the elusive silanol family. The SiH 3 OH 2 + ion is generated in a silane/water plasma expansion, and its structure is derived from the IR photodissociation (IRPD) spectrum of its Ar cluster measured in a tandem mass spectrometer. The chemical bonding in SiH 3 OH 2 + is analyzed by density functional theory (DFT) calculations, providing detailed insight into the nature of the dative H 3 Si + ‐OH 2 bond. Comparison with protonated methanol illustrates the differences in bonding between carbon and silicon, which are mainly related to their different electronegativity and the different energy of the vacant valence p z orbital of SiH 3 + and CH 3 + .