Is There an Adduct of Pyridine N-Oxide and Boron Trifluoride in the Gaseous State? Gas Electron Diffraction vs Mass Spectrometry

Abstract

A study of saturated vapor over the pyridine N-oxide-boron trifluoride (PyO-BF 3 ) adduct was carried out at T = 448(5) K by a synchronous gas electron diffraction/mass spectrometry (GED/MS) experiment. Due to the absence of ions in the mass spectrum, indicating the presence of a structure with an O−B dative bond, several models of vapor composition were tested by the GED method. It was found that the dominant molecular form (up to 100%) in vapor is the PyO-BF 3 adduct. Using the DFT/M06-2X/aug-cc-pVTZ method, geometric optimization of the molecular ion [PyO-BF 3 ] + was carried out, which showed its intrinsic instability and dissociation into a [PyO] + cation and a BF 3 molecule. This study certainly demonstrates the significant advantage of the GED method to determine the qualitative and quantitative gas-phase composition of dative-bonded adducts and other noncovalent complexes as well, whereas the interpretation of mass spectra may be ambiguous due to the possible intrinsic instability of ions containing a dative bond. The nature of the O−B bond is discussed in terms of the natural bond orbitals (NBOs) and the quantum theory of atoms in molecules (QTAIM). A comparison of structural and energetic parameters for PyO-BF 3 and the previously studied BF 3 adducts allows the theoretical comprehension of the nature of the O−B bond to be extended and to explain the different thermal stabilities of these compounds.