Reactions of Sn(NMe2)2 with Primary Aryl Phosphides, ArPH-: Synthesis and Structures of the Heteroleptic Cages [{(PhP−PPh)Sn(μ-PPh)}2(Na·PMDETA)4 and [{Sn(μ3-Ppy)}3{Sn(μ3,μ1-pyP−Ppy)}3]

The reaction of Sn(NMe2)2 with the primary phosphido alkali metal complex PhPHNa (1:2 equiv, respectively) in the presence of the Lewis base donor PMDETA [(Me2NCH2CH2)2NMe] gives the heterometallic cage [{(PhP−PPh)Sn(μ-PPh)}2(Na·PMDETA)4 (1), containing the novel [(PhP−PPh)Sn(μ-PPh)]24- tetraanion. The analogous reaction using pyPHLi (py = 2-pyridyl) in THF/toluene as the solvent gives the neutral cage [{Sn(μ3-Ppy)}3{Sn(μ3,μ1-pyP−Ppy)}3] (2), having a unique “stacked” propeller arrangement in the solid state.