Über Umsetzungen von weißem Phosphor mit Metallorganylen

Reactions of White Phosphorus with Lithium Alkyls The reaction of white phosphorus with Lime (me = CH₃) (molar ratio P₄: Lime = 1:1) in DME or THF via insoluble lithium polyphosphides yields Li₃P₇ 1 , Li₂P₇me 2 and LiP₇me₂ 3 , which react with me₃SiCl or meBr to form P₇(Sime₃)₃, P₇(Sime₃)₂me and P₇me₃, respectively. All of these compounds were characterized by ³¹P-n.m.r. By higher amounts of Lime (molar ratio P₄:Lime = 1:2) Li₂P₇me is decomposed. The analogous reaction of P₄ with LiCme₃ yields Li₃P₇, LiP₇(Cme₃)₂, Li₂P₇Cme₃, and additionally LiP₄(Cme₃)₃ and LiP₃(Cme₃)₂. Again insoluble lithium polyphosphides were observed as intermediates. Addition of me₃SiCl to the reaction mixture affords P₇(Sime₃)₃, P₇(Sime₃)₂(Cme₃), P₇(Sime₃)(Cme₃)₂ P₄(Sime₃)(Cme₃)₃, and P₃(Sime₃)(Cme₃)₂. In n-hexane/THF the reaction of P₄ with LiCme₃ in the molar ratio of 1:2 predominantly yields the fourmembered ring LiP₄(Cme₃)₃ besides some of the three-membered ring LiP₃(Cme₃)₂, which with me₃SiCl yield P₄(Sime₃)(Cme₃)₃ and P₃(Sime₃)(Cme₃)₂. In addition to the mentioned main products are found: all compounds of the group P₈(Sime₃)₅(Cme₃) to P₈(Sime₃)(Cme₃)₅, the five-membered rings P₅(Sime₃)₂(Cme₃)₃ and P₅(Sime₃)₃(Cme₃)₂ as well as P(Sime₃)₂Cme₃ and P(Sime₃)₃.     

Über die Reaktion von weißem Phosphor mit Jodwasserstoff

White phosphorus and hydrogen iodide quantitatively form PH₃ and P₂J₄ in anhydrous carbon disulfide. Besides PJ₃ the hitherto unknown iodophosphines PH₂J and PHJ₂ are formed during the reaction as intermediates.     

Cyanphosphorverbindungen. IX. Cyanidabbau von weißem Phosphor zu Dicyanphosphiden und die Dicyanphosphid-Struktur

Cyanophosphorus Compounds. IX. Breakdown of White Phosphorus by Cyanide Yielding Dicyanophosphides and Dicyanophosphide Structure White phosphorus is degraded by strong enough anionic nucleophiles X^? with more or less disproportionation. With crown ether alkali, ammonium or phosphonium cyanides, X^? = CN^?, selectively the corresponding dicyanophosphide, P(CN)₂^?, is formed and a polyphosphide, preferentially P₁₅^?. [18] Crown-6-KP(CN)₂ is also obtained from the reaction of P(CN)₃, KF, and crown ether. In the crystal of this salt the dicyanophosphide anions (bent at phosphorus by an angle of 95°) coordinate with both nitrogen ends towards (different) cations. The PC distance (168 pm on the average) is as short as in phosphaalkenes. δ¹³C and J_PC of P(CN)₂^? fit well into a correlation with the charge density at phosphorus generally valid for cyanophosphorus compounds.