Abstract

The 1-halogeno-1,3,5-triazinium hexafluoroarsenate and hexafluoroantimonate compounds of the type [(HCN) 3X][MF 6] (MAs; XF, ( 1), Cl ( 2) and MSb; XBr ( 3)) have been synthesized by direct reaction of 1,3,5-triazine, (HCN) 3, with halogenomonofluorides, XF, in the presence of AsF 5 or SbF 5, respectively. The reactions of (HCN) 3 and malonitrile, CH 2(CN) 2, with [I 3][AsF 6 afforded the iodonium adduct species [{(HCN) 3} nI][AsF 6] ( n=1 ( 4), 2 ( 5)) and [{CH 2(CN) 2} nI][AsF 6] ( n=1 ( 6), 2 ( 7)). All compounds have been characterized by chemical analyses, proton NMR spectroscopy and vibrational spectral data (IR, Raman). Temperature dependent 1H NMR spectroscopy on SO 2 solutions of 1– 3 revealed functional behaviour at room temperature which was frozen down at −60 °C (two resonances, ratio 1:2). According to the NMR the scale the cations in 4 and 5 exist already in the slow exchange region at room temperature. Solution behaviour, IR and UV data of 6 (naples yellow reddish) and 7 (black) suggest 7 to be polymeric and 6 to be monomeric with strong intermolecular I···I interactions.

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