Henicosaphosphide

TRILITHIUM HEPTAPHOSPHIDE, DILITHIUM HEXADECAPHOSPHIDE, AND TRISODIUM HENICOSAPHOSPHIDE... 

Trilithium heptaphosphide, dilithium hexadecaphosphide, and trisodium henicosaphosphide are polyphosphides with isolated anions in the solid state as well as in solution. These metalated poly phosphorus compounds are of interest because of their structural relationship to the phosphorus hydrides (phosphanes) and organophosphanes P.R and particularly because of their potential use as building blocks for the syntheses of polyphosphorus compounds. 

Trisodium henicosaphosphide is obtained using equipment similar to that... 

Trisodium henicosaphosphide is obtained as an adduct with 15 mol of THF and forms orange needle-shaped crystals, which liquefy above — 10°C. At room temperature the melt undergoes a slow disproportionation. The crystals are slightly sensitive to oxidation but strongly sensitive to hydrolysis. A solution of NajPji in THF-DMF ( 2 1) exhibits a P NMR spectrum with seven signal groups at d + 72, -1-61, — 15, -108,-118, —146, and... 

In the alkylation or silylation of trisodium henicosaphosphide the monometalated henicosaphosphanes(3) NaP2iR2 [R = CH3, C2H5, J-C3H7, and (CH3)3Si] have been obtained as the final products. A substitution on the central one-atom bridge of the P2i ion does not occur for steric reasons. 

The stability of the heptaphosphanortricyclene cage is emphasized by its presence as the terminal group in trisodium henicosaphosphide Na3P21, which is preferentially silylated terminally rather than at the middle phosphide atom to give 54 (equation 53)68. 

NaPsWwOiiii], tetradecaammonium, hentricontahydrate, 27 115 Sodium, cyclopentadienyl-, compound with l,2-dimethoxyethane(l l), 26 341 Sodium henicosaphosphide. (Na.,P.[Pg.368]

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