Nucleophilic Degradation of White Phosphorus with tBu3SiK: Synthesis and X-ray Crystal Structure Analysis of the Potassium Triphosphide (tBu3Si)2P3K

The potassium phosphides ( t Bu 3 Si) 2 P 4 K 2 and ( t Bu 3 Si) 4 P 8 K 4 can be synthesized from the reaction of P 4 with 2 equiv of the potassium silanide t Bu 3 SiK in tetrahydrofuran at −78 °C. The potassium silanide t Bu 3 SiK slowly transforms the tetraphospide ( t Bu 3 Si) 2 P 4 K 2 and the octaphosphide ( t Bu 3 Si) 4 P 8 K 4 into ( t Bu 3 Si) 2 P 3 K and ( t Bu 3 Si) 3 P 5 K 2 . X-ray quality crystals of the triphosphide, t Bu 3 SiKP−P PSi t Bu 3, have been obtained from a tetrahydrofuran solution at −25 °C.