A P4 Chain and Cage from Silylene-Activated White Phosphorus


  • H.W.R. thanks the Deutsche Forschungsgemeinschaft (DFG RO 224/55-3) for support. S.K. is indebted to the DAAD for a research fellowship. D.S. is grateful for funding from the DFG Priority Programme 1178, the DNRF-funded Center for Materials Crystallography (CMC) for support, and the Land Niedersachsen for providing a fellowship in the Catalysis for Sustainable Synthesis (CaSuS) Ph.D. program.


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An acyclic P4chain supported by a silicon-substituted amidinato ligand was formed from the reaction of PhC(NtBu)2SiN(TMS)2 with P4 (TMS=Me3Si). This is the first example of an acyclic Si[BOND]P chain that contains 6π electrons. When the benzamidinato moiety was replaced with Cp* (Cp*=Me5C5), an unusual silicon–phosphorus cage surprisingly formed (see scheme).