Synthesis and Metallation of the Diphosphanylsilane i Pr 2 Si(PHMe) 2

The reaction of [LiAl(PHMe) 4 ] with i Pr 2 SiCl 2 yields the dialkyldiphosphanylsilane i Pr 2 Si(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(SiMe 3 ) 2 } 2 ] and [Zn{N(SiMe 3 ) 2 } 2 ] to form the polycyclic compounds [Sn{SnN(SiMe 3 ) 2 } 2 { i Pr 2 Si(PMe) 2 } 2 ] ( 2 ) and [{ZnN(SiMe 3 ) 2 } 3 { i Pr 2 Si(PMe) 2 } 2 H] ( 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 Zn 3 P 4 Si 2 cage. The compounds [ i Pr 2 Si{P(Me)MEt 2 } 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 MEt 3 (M = Al, Ga). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)