Beiträge zur Chemie des Phosphors. 151. Dilithium‐dihydrogentetradecaphosphid, Li₂H₂P₁₄: Darstellung und strukturelle Charakterisierung

Abstract

Dilithium‐dihydrogentetradecaphosphid, Li2H2P14 (1), wird durch Metallierung von P2H4 mit n‐BuLi unter geeigneten Bedingungen als orangerotes Lösungsmitteladdukt Li2H2P14 · 6 THF in 80 bis 90proz. Reinheit erhalten. 1 entsteht außerdem bei der Reaktion von Li3P7 oder LiH4P5 mit P2H4 und bei der Disproportionierung von LiH4P7. Entsprechend dem 2D‐31P‐NMR‐Spektrum ist 1 als Konjunkto‐Phosphan aus einem P7(5)⊖‐ und einem P9(3)⊖‐Teilgerüst mit Norbornan‐ bzw. Deltacyclan‐analoger Struktur aufgebaut.

Solution phase synthesis of the less-known Form II crystalline red phosphorus

“…4f). 29,47 According to the "dissolution-crystallization" mechanism proposed in an earlier work by our group, 48 the phenomena that the early-stage rise and then fall of the concentration of polyphosphide clusters indicate their possible role as the crucial reaction intermediates. Additional evidence was provided by time-dependent microscopic morphological variation of the reaction products (Fig.…”

Hydrogen Polyphosphides P3H23−and P3H32−: Synthesis and Crystal Structure of K3(P3H2)·2.3NH3, Rb3(P3H2)·NH3, [Rb(18-crown-6)]2(P3H3)·7.5NH3, and [Cs(18-crown-6)]2(P3H3)·7NH3

“…The crystal structure features hydrogen bonds between the hydrogen atoms H (7), H (8), and H(9) of the ammonia molecule with nitrogen atom N(3) and the oxygen atoms O(8), O(9), O (10), and O(12) of a crown ether molecule (Figure 9). Furthermore, the nitrogen atom N(5)#1 of an ammonia molecule is bound via H(11)#1 to O(9) (Figure 9).…”

“…Most of the hitherto known hydrogen polyphosphides are thermally unstable, highly unstable to pH change, or both. Baudler and coworkers were the first who could identify several hydrogen polyphosphides using solution NMR methods. − Recently, direct synthetic routes to stable, crystalline hydrogen polyphosphides were elaborated and led to compounds with P 7 H 2 − , P 7 H 2− , and P 11 H 2− anions, − which were characterized by X-ray structure analysis. The reactions leading to these hydrogen polyphosphides were carried out by dissolving the corresponding alkali metal polyphosphides in liquid ammonia and protonating the anions under very controlled conditions in the presence of voluminous counterions.…”