The 31P- and 1H-NMR spectra of PH3, PD3, P2H4, P2D4, P3H5, and of a mixture of higher phosphanes were investigated at -60° to -93°C. The chemical shifts of the 31P-spectra were determined against TMS by means of INDOR measurements and converted to the shifts against 85% H3PO4 at 30°C using (CH3O)3P as an auxiliary substance. By the same method a P4O6/CS2 solution was calibrated as a 31P-low temperature standard.While liquid P2H4 exhibits no remarkable association, it shows an obvious influence on PH3 dissolved in it. By means of double resonance experiments the equivalency of protons in P2H4 could be demonstrated as well as the AB2 system expected for P3H5

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Bei dcr Oaydatron voti CF.$JlP(Cc,lis)2 (1) mit 0 2 i n I oluol, Bcii~ol, Hexadeutcrobcnaol odcr n-Hexan entsteht gemafj GI. f 1) be1 Raumtemperdtur in einem durch die elektronenziehende CF~-Gruppe bedingten komplizierten Reaktionsablauf der Diplienylphorpliinsaiire-[l-diphenylphosphoryI-2.2.2-trifluor-athyIester] (2) und COz. Wahrend die Summenformel der Verbindung aus der E~ementardnalysc und dem Massenspektrurn hervorgeht. lasen sich die wesentlichen Bcstdndteile von 2 durch alkalische Hydrolyse entsprechend den Gleichungen (2) und ( 3 ) crniitteln. Die Struktur von 2 ergab sich welterhin durch ausfuhrliche 1 H-. "Jr-untl 31P-NMR-SOWIF IR-qxktrosl\opische Untersuchungen. the Behaviour of rrifluoroacetyldiphenylphosphine towards Molecukdr OxygenThe oxidation of CF3COP(ChH~)z (1) with 0 2 in toluene, benzene, hexadeuterobenzenc or n-heuane at room temperature yields d~phenylphosphinic acid [l-diphenylphosphory1-2,2,2-trif1rioroeth)I) ester (2) and COz according to equation (I). The course of the reaction is complicated because of the presence of the electron-attracting CF3-group. While the cmpirical formula of thecompound is obtained from elementary analysisand mass spectra, the essential components of 2 are determined by means of alkaline hydrolysis according to equation (2) and (3). The structure of 2 was confirmed by extensive IN, 19F, 31P n. m. r. and i. r. spectroscopic invcstigations.

The changes of 31 P nuclear magnetic resonance spectra of P2I4-CS2 solutions and of molecular weights of P2I4 in benzene with time have shown that in inert solvents a gradual disproportionation occurs with formation of PI3 . White Phosphorus, P4 , is not formed by this process. Instead the initially formed disproportionation product with higher Phosphorus content changes into a polymeric solid PnI by cleavage of PIS , which accounts for the increasing displacement of disproportionation equilibrium. The UV spectrum of P2I4 in n-Hexan is reported. The molar extinction coefficients indicate a considerable derealization of unshared electron pairs of the Phosphorus atoms.

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