From the reaction of white phosphorus with sodium (P: Na = 3:1) in boiling THF or monoglyme (2‐3 h) in the presence of 18‐crown‐6 the solvent adduct Na2P16·3(18‐crown‐6)·2 THF (or a monoglyme adduct) is obtained.

022ChemInform Abstract The reaction of white phosphorus with Na in liquid ammonia yields the title compounds besides other products (mainly NaPH2 and Na2HP7). 31P NMR spectroscopic results show that of the three possible diastereoisomers only the erythro,erythroisomer (I) with transoid NH2 groups is formed. The compound is only stable in liquid ammonia.

Während Na3P21 bei der Umsetzung von weißem Pmit Na in THF gebildet wird, entsteht Li3P21 (nicht isoliert) bei der Reaktion von Li3P7 mit Iod oder 1,2‐Dibromethan sowie bei der Metallierung von P7H3 mit Li‐dihydrogenphosphid oder n‐Butyllithium.

structure structure (solids and liquids) D 2000 -011Contributions to the Chemistry of Phosphorus. Part 225. Lithium Pentahydrogen Octaphosphide.-The title compound (III) is one of the first reaction products from the metalation of P2H4 with nBuLi that has been detected. Additionally LiH4P7, LiH8P7, LixHyPz and some further polyphosphides are formed. ( III) can also be obtained by reaction of Li3P7 or LiH4P5 with P2H4 at -25 • C and -78 • C, respectively. At -78 • C (III) is stable in the product mixture and decomposes at room temp. to Li2P16 and PH3 and some Li3P21 and Li3P19. The composition and structure of (III) are determined by 31P NMR studies, especially analysis of its low-temp. 31P(1H) NMR spectrum. -(BAUDLER, M.; HEUMUELLER, R.; DUESTER, D.; Z.

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