Novel compositions are provided containing a compound represented by the formula YOSF5 or ZOSF5, where: (a) Y is: (i) an organic cation other than (Me2N)3S+ or (ii) an inorganic cation, provided that when Y is the inorganic cation, the composition further includes a complexing agent; and (b) Z is C1-20 alkyl, aryl, cycloalkyl, combinations thereof, or analogues thereof containing at least one heteroatom, provided that the compound represented by the formula ZOSF5 is a molecular compound. Processes of making the cationic compounds are disclosed as are processes for using the compositions containing cationic compounds in nucleophilic replacement reactions to prepare the compositions containing molecular compounds including the OSF5 group.