Central Institute of Inorg. Chem. Acad. of Sci., Berlin, GDR;Kurnakov Institute, Acad. of Sci., Moscow, USSR
Abstract:
Nitriles react with PF5 and also with AsF5, SbF5 forming 1:1-adducts. Using C2Cl3F3 as a solvent is of advantage for this reaction. PF5·CH3CN and N(C2H5)4]SH give N(C2H5)4]P2S2F8] with a sulfur double bridge and hexafluorophosphate in acetonitrile 1]. In case of AsF5·CH3CN a salt with the anion AsF5NHCSCH3]? has been isolated 2]. Following products have been confirmed in a reaction mixture of PF5·CH3CN and SH? in acetonitrile by NMR (31P and 19F): PF6]?, F5PSPF5]2?, , F4PSH, F3PS, HPS2F2, PS2F2]?, F5PNC(SH)CH3]?, F5PNHCSCH3]?, F5PSH]?. With a ratio PF5·CH3CN: SH? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products.
