Derivatization of Tris(trimethylsilyl)heptaphosphane

Through SiP bond cleavage, the reaction of P₇(SiMe₃)₃ with one equivalent of KO^tBu or LiO^tBu afforded different isomers of the heptaphosphanide anion [P₇(SiMe₃)₂]⁻. With LiO^tBu, concomitant inversion at an equatorial (silylated) phosphorus atom occurred and the C_s symmetric isomer characterized by a mirror plane formed. With KO^tBu, inversion did not occur and the resulting asymmetric anion with C₁ symmetry formed. With NaO^tBu, a mixture of both isomers was obtained. The symmetries and structures of the anions were elucidated with ³¹P{¹H} and ²⁹Si{¹H} NMR spectroscopy, and relative stabilities were calculated employing the B3LYP/6-31+G* method.The reaction of KP₇(SiMe₃)₂ or LiP₇(SiMe₃)₂ with 1,2-dichlorotetramethyldisilane led to (SiMe₃)₂P₇SiMe₂SiMe₂P₇(SiMe₃)₂, a molecule composed of two P₇-cages connected by a disilane bridge. It can also be obtained through silyl exchange using P₇(SiMe₃)₃ and ClMe₂SiSiMe₂Cl. The compound was characterized with ³¹P and ²⁹Si-NMR spectroscopy and elemental analysis. Treatment of P₇(SiMe₃)₃ with HypCl (Hyp = hypersilyl = Si(SiMe₃)₃) in DME led to the quantitative formation of Hyp₂P₇SiMe₃. Single crystal X-ray diffraction as well as ³¹P and ²⁹Si-NMR spectroscopy proves the presence of a heteroleptically substituted heptaphosphane cage.Quantum chemical HF and B3LYP/6-31G* calculations of equilibrium structures for the two possible isomers of P₇(SiMe₃)₃ (sym and asym) reveal that asym is destabilized by about 30-40 kJ mol⁻¹, which explains why its formation could not be observed. The phosphorus inversion barrier for the sym → asym transition is calculated as 60-70 kJ mol⁻¹.