Beiträge zur Chemie des Phosphors, 49.

Abstract

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

Retrodienic reactions. Part 2. Vinyl- and propenyl-phosphines: synthesis by flash vacuum thermolysis and characterization

“…for C,8Hl,0,P: M , 314.1072); vmaX,(CCl4) 2 950, 1 460, 1 285, 1 242, 1 062, and 1 040 cm-'; G,(CDCI,) 1 . (16).-Cyclopentadiene (0.6 g, 9.1 mmol), diethyl prop-l-enylphosphonate (7) (1.20 g, 6.74 mmol) and hydroquinone (0.1 g) were heated at 175 "C for 18 h in a sealed tube and the reaction product was purified by column chromatography on alumina. After the impurities had been eliminated with pentane-ther (7: 3), elution with ether gave the phosphonate (16) 10) and ( 13)-( 16): Preparation qf the Phosphines (17)-( 22).…”

“…On reduction with lithium aluminum hydride xhlorotrimethylsilane,'5 the phosphonates @-(lo) and (13)- ( 16) were converted into the corresponding primary phosphines (17)-( 22) (yield 6&80%) (Schemes 4, 5, and 6). However, owing to their low thermal stability and high air sensitivity, these phosphines were characterized and used without complete purification (see the Experimental section).…”

Electrochemical Lithium Extraction and Insertion Process of Sol-Gel Synthesized LiMnPO4via Two-Phase Mechanism

“…some Li-H exchange. 62,63 Fig. 11 a) 7 Li and b) 31 P MAS NMR spectra of LMP/C samples at different state of charge, acquired at a spinning speed of 60 kHz and a recycle delay of 1 s. Spinning sidebands are marked with an asterisk, a plus sign, and a cross.…”

Beiträge zur Chemie des Phosphors, 145 [1]. Neue Lithium-hydrogenpolyphosphide durch Metallierung von Diphosphan / Contributions to the Chemistry of Phosphorus, 145 [1]. Novel Lithium Hydrogen Polyphosphides Through Metalation of Diphosphane

“…Das 31P{1H}-NM RSpektrum dieser Lösung (A bb. la ) zeigt neben den Signalen von PH 3, P2H 4 und P3H 5 [7] die Spinsysteme von vier H auptm etallierungsprodukten, von denen drei zugeordnet w erden konnten. Es handelt sich um die drei Signalgruppen von LiH4P7 (T ) [8], die acht teilweise verdeckten und sich überlagernden G rup pen von LiH 5P8 (V) [8] und die drei G ruppen von LiH 8P7 (□ ) [8].…”