Synthesis and Structural Characterization of New Polyphosphorus Ring and Cage Compounds

The 1:1 and 2:1 reactions of (Me(3)Si)(2)PLi.2THF with several amino chlorophosphanes have been surveyed. With (i)()Pr(2)NPCl(2), both reactant stoichiometries produce the four-membered ring compound (3) via different reaction schemes. Compound 3 combines with Fe(2)(CO)(9) to produce a monometallic complex (4) in which the Fe(CO)(4) fragment is bonded to one of the Me(3)SiP centers. With the cyclic hydrazino phosphane ClP(MeNNMe)(2)PCl only the bis-phosphane substitution product, (Me(3)Si)(2)PP(MeNNMe)(2)PP(SiMe(3))(2), is isolated. With the cyclic diazadiphosphetidine ((t)()BuNPCl)(2) a bis-phosphane substitution product [(t)()BuNPP(SiMe(3))(2)](2) (10) is formed along with a cage compound [((t)()BuNP)(2)P(SiMe(3))](2) (11). The new compounds have been characterized by spectroscopic techniques, and the molecular structure of 4 and 11 have been determined by X-ray crystallography.