[en] NMR of ¹⁹F is used to study reactions of tungsten fluoride with ethylene glycol, 1,2- and 1,3-propanediol and 2,3-butanediol. As a result, dimer, trimer and tetramer compounds with four or five fluorine atoms are obtained, in which tungsten atoms are bound by deprotonated diol groups, there with each metal atom is bound to others by only one such group. With the corresponding diol concentration dimer compounds in which two tungsten atoms are bound by two bridge deprotonated diol groups are formed. With increase of diol: WF₆ ratio monomer octahedral tungsten compounds with three fluorine atoms are formed. Parameters of NMR ¹⁹F spectra of obtained compounds are determined