Untersuchungen an P₄O₇: Ein neues Darstellungsverfahren, Strukturdaten und schwingungsspektroskopische Charakterisierung

Abstract

Die Darstellung von reinem P4O7 in einem Schritt gelingt durch Oxydation von P4O6 im geschlossenen System unter „sauerstoffgepufferter”︁ Atmosphäre. Es werden die vollständigen Strukturdaten mitgeteilt. Eine Zuordnung der Schwingungsspektren (Raman und IR) wird auf der Basis von Messungen am orientierten Einkristall und von Vergleichen mit P4O6 und P4O10 vorgeschlagen.

P8O12·2BH3 − The Borane Adduct of a New Molecular Phosphorus Oxide

“…[23Ϫ25] Although quantum chemical calculations for P 4 O 6 X (X ϭ O, S, H ϩ , F ϩ , Cl ϩ , N Ϫ ) [26] indicate a strong dependence of the PϪO cage bond lengths on the electronegativity of terminal atoms attached to the phosphorus atom, very similar geometrical parameters have been found for the P 4 O 6 cages of P 4 O 7 , [2,3] P 4 O 6 S, [7] P 4 O 6 Se, [11] and P 4 O 6 Fe(CO) 4 . [18] Up to now, this observation and the different behavior of P 4 O 6 NR in comparison with P 4 O 6 X (e.g.…”

“…[28,29] If pure liquid P 4 O 6 is used, electrophilic addition stops at the stage of P 4 O 6 ·2BH 3 due to crystallization. [27] 3 are applied. The NMR spectroscopic data of these compounds (see Exp.…”

“…Due to packing effects the point symmetry C 2h , expected for free P 8 O 12 ·2BH 3 molecules, is reduced to C 1 in the crystalline solid. As a consequence, the two bicyclic P 4 As there are no other phosphorus compounds known that have a similar structure, we are restricted to comparing the geometric parameters of 1 with those of P 4 O 6 X (X ϭ O, S, Se) and (RO) 3 [a] Refs. [2,3] [b] Ref.…”

“…1 was characterized by means of X-ray diffractometry (powder, single crystal), NMR spectroscopy (solution, solid), IR spectroscopy, Raman spectroscopy, and mass spectrometry. Mass spectrometric investigations suggest considerable BH 3 abstraction as well as an enhanced stability of P 8 In contrast to chalcogen atoms, the electrophilic addition of BH 3 is expected to affect the cage bonds in a different manner due to the reduced π-donor abilities of boron. For this reason we have tried to synthesize and characterize borane complexes of P 4 O 6 , the constitutions of which were previously studied by 31 P NMR spectra of solutions.…”

“…[7Ϫ10] P 4 O 6 Se n (n ϭ 1Ϫ4), [11Ϫ14] and transition metal complexes like P 4 O 6 [Ni(CO) 3 ] n (n ϭ 1Ϫ4), [15,16] P 4 O 6 -[Fe(CO) 4 ] n (n ϭ 1Ϫ4), [17,18] and P 4 O 6 [M(CO) 5 ] (M ϭ Cr, Mo, W). [19] On the other hand, ring-opening reactions are much more difficult to control and normally lead to complete degradation of the framework.…”