R o o m temperature reactions o f

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ABSTRACT

The reaction of S4N4 with Ph2PCl (1:3 molar ratio) in boiling acetonitrile produces the six-membered ring (Ph2PN)2(NSCl) in excellent yield. The salt [Ph2P(Cl)N(Cl)PPh2]+Cr is the major product when the molar ratio is increased to 1:12. The reactions of S4N4 with PC13 or PhPCl2 (1:3 molar ratio) also give heterocycles containing the P2SN3 ring. Derivatives of the type (Ph2PN)2(NSX) (X = I, Ph, NR2 (R = Me, Et, -(CH2)5-)) are obtained by treatment of (Ph2PN)2(NSCl) with KI, Ph2Hg, Me3SiNMe2, Et2NH, or CSH10NH, respectively, in acetonitrile. The cation [(Ph2PN)2(SN)]+ is prepared as a trihalide salt by addition of halogens (Br2 or I2) to (Ph2PN)2(NSCl). Thermolysis at 155 °C or treatment with Ph3Sb converts [(Ph2PN)2(SN)]+Br3" to (Ph2PN)2(NSBr). The halides (Ph2PN)2(NSX) (X = Cl, Br, I) are readily hydrolyzed to [Ph2P(NH2)N(NH2)PPh2]+X" in air.

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