Syntheses, characterisation, and computational studies of tungsten hexafluoride adducts with pyridine and its derivatives

Abstract

The reactions of WF6 with pyridine, 4-methylpyridine, 4-(dimethylamino)pyridine, and 4,4′-bipyridine (4,4′-bipy) in CH2Cl2 afford the Lewis-acid-base adducts WF6(4-NC5H4R) (R = H, CH3, N(CH3)2) and F6W(4,4′-bipy)WF6 as solids in quantitative yields. These adducts have been characterised in the solid state by Raman spectroscopy at ambient temperature and, in the cases of the mononuclear adducts, by X-ray crystallography at −173 °C. Furthermore, density-functional-theory (DFT-B3LYP) studies have been conducted to aid in predicting the structure of F6W(4,4′-bipy)WF6, assigning the vibrational frequencies of the adducts, and comparing their electronic properties.