Beiträge zur Chemie des Phosphors. 157. Dilithium‐hexadecaphosphid, Li₂P₁₆: Darstellung aus Li₂HP₇ und ³¹P‐NMR‐spektroskopische Strukturbestimmung

Abstract

Dilithium‐hexadecaphosphid, Li2P16 (1), wird bei der Disproportionierung von Li2HP7 in Tetrahydrofuran unter geeigneten Bedingungen als kristallines Lösungsmitteladdukt Li2P16 · 8 THF rein erhalten. Die Konstitution von 1 wurde aus dem 1D‐ und 2D‐31P‐NMR‐Spektrum (in Dimethylformamid) abgeleitet. Das P162−‐Ion hat in Lösung die gleiche Struktur wie in festem (Ph4P)2P16 [20]. Es ist als Konjunkto‐Phosphan aus zwei P9(3)⊖‐Teilgerüsten mit Deltacyclananaloger Struktur aufgebaut, die über die Zweierbrücke als gemeinsame Nullbrücke miteinander verbunden sind.

From Clusters to Unorthodox Pnictogen Sources: Solution-Phase Reactivity of [E7]3–(E = P–Sb) Anions

“…In contrast to [P 14 ] 4– and [P 21 ] 3– , this was first prepared by reaction of P 4 with LiPH 2 or oxidation of [P 7 ] 3– with [PPh 4 ]­[Cl] . Baudler and co-workers later reported the synthesis via disproportionation of Li 2 [HP 7 ]. , The 31 P NMR spectrum shows resonances at 60, 38, 6, −34, −134, and −180 ppm integrating in the ratio 2:1:1:1:1:2.…”

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

“…We began our investigation of Pred activation by surveying approaches that were previously used for the activation of Pwhite to polyphosphides with alkali metals, [12] LiPH2, [13][14][15][16] or sodium naphthalenide [17] . By reacting Pred with potassium metal in refluxing THF/DME (1:1 v/v), we were able to obtain orange-red solutions that contained a mixture of soluble polyphosphide anions, P5 -, P16 2-, and P21 3-, according to the 31 P NMR spectra (Figure 1a).…”

A new route for the metallation of trihydroheptaphosphine P7H3 with butyllithium

“…The selective formation of dilithium hexadeca phosphide was also observed for the thermal decomposi tion of Li 2 HP 7 (see Ref. 13). Probably, in the metallation of heptaphosphine 1 with BuLi, the hydrogen atoms are partially substituted for the metal cations to form the dilithium derivative of heptaphosphine, which is trans formed into Li 2 P 16 (2) at room temperature.…”