Cage Compounds of Phosphorus and the Heavier Group 14 Elements

The Sn/P cage compounds Sn₁₀(tBuP)₄] ( 1 ) and Sn₁₀(tBuP)₇Cl₄] ( 2 ) were obtained by the reaction of LitBuPH with SnBr₂ and SnCl₂, respectively. Theoretical calculations confirm that the tin atoms in 2 feature different formal oxidation states. The reaction of PbCl₂ with LitBuPH and LiPHSiiPr₃ yields the Pb/P cage compounds Pb₇(tBuP)₇] ( 3 ) and Pb₆(PSiiPr₃)₆] ( 4 ), respectively, that represent new derivatives of known polyhedrons of this class of compounds. The new products were characterized by X‐ray diffraction, elemental analysis and partially by MS and MAS‐NMR spectroscopy.