Synthesis and Metallation of the Diphosphanylsilane iPr2Si(PHMe)2

The reaction of [LiAl(PHMe)4] with iPr2SiCl2 yields the dialkyldiphosphanylsilane iPr2Si(PHMe)2 (1). This compound is formed as a diastereomeric mixture and was identified by NMR spectroscopy and mass spectrometry. Silane 1 reacts with [Sn{N(SiMe3)2}2] and [Zn{N(SiMe3)2}2] to form the polycyclic compounds [Sn{SnN(SiMe3)2}2{iPr2Si(PMe)2}2] (2) and [{ZnN(SiMe3)2}3{iPr2Si(PMe)2}2H] (3), respectively. The tricyclic compound 2 possesses one Sn–Sn bond and contains tin atoms in the formal oxidation states +1, +2 and +3. The central structural motif of the zinc–phosphorus cluster 3 is a Zn3P4Si2 cage. The compounds [iPr2Si{P(Me)MEt2}2]2 (4: M = Al; 5: M = Ga), which feature an adamantane‐like cage formed by four metal, four phosphorus and two silicon atoms can be obtained by the reaction of 1 with MEt3 (M = Al, Ga). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)