Pentachloride phosphines

Phosphine oxides, e.g., di-/ -octadecylphosphine oxide, are oxidized to phos-phinic acids by hydrogen peroxide. With chlorine or phosphorus pentachloride, phosphine oxides form dialkylphosphinyl chlorides, R2P(0)C1, which can be easily hydrolyzed to phosphinic acids [162,165] see Eqs. (96) and (97) ... 

OSMIUM TETROXIDE - WHITE PHOSPHORUS - WHITE PHOSPHORUS TRICHLORIDE PHOSPHORUS PENTACHLORIDE PHOSPHINE... 

Chlorine dioxide Ammonia, carbon monoxide, hydrogen, hydrogen sulflde, methane, mercury, nonmetals, phosphine, phosphorus pentachloride... 

Phosphine Phosphoric acid Phosphorus (yellow) Phosphorus pentachloride... 

The reactions of phosphorus pentachloride and diphenyltrichloro-phosphorane with amines and related compounds are reported in Chapter 9. The n.m.r. spectra of phosphine-phosphorus pentafluoride adducts have been described (see Chapter 11 for details). 

A. Nucleophilic Reactions of the P=0 Group.—Tris(trifluoromethyl)-phosphine oxide (33) reacts with hexamethyldisiloxane to give a phos-phorane, whose n.m.r. spectrum at — 140 °C shows non-equivalent trifluoromethyl groups. Although this unusual reaction clearly involves nucleophilic attack of the phosphoryl oxygen on silicon at some stage of the reaction, a full study of the mechanism has not been published. Tertiary phosphine oxides can be converted cleanly into dichlorophos-phoranes (34) by treatment with two moles of phosphorus pentachloride. Alkylation of the sodium salt of tetraphenylmethylenediphosphine dioxide (35) with alkyl halides, in dimethyl sulphoxide, has been reported to... 

Protactinium (continued) pentachloride, 12 10, II complexes with phosphine oxides, 12 30, 31... 

Antimony Trichloride Antimony Trichloride Antimony Pentachloride Antimony Pentachloride Antimony Pentafluoride Antimony Pentachloride Antimony Potassium Tartarate Antimony Trichloride Antimony Trifluoride Antimony Trioxide Benzene Hexachloride Benzene Hexachloride Tris(Aziridinyl) Phosphine Oxide Ammonium Hydroxide Thiram... 

Tetrakis(phenyldifluorophosphine)nickel-(0) could also be obtained, using arsenic trifluoride in the presence of catalytic amounts of antimony pentachloride, or zinc fluoride as fluorinating agents. Yields as high as 50% could be obtained, but sizable decomposition on the process of fluorination of the chlorophosphine nickel-(0) complexes in solution could not be entirely suppressed. The marked instability of zerovalent nickel-phosphine complexes in solution in organic solvents, even under strictly anhydrous and anaerobic conditions, has been noted by several workers (16,20), but is still lacking a detailed explanation. A closer examination of the system carbon tetrachloride-tetrakis(trichlorophosphine)nickel-(0) (23) showed the main pa h of the reaction to consist in the formation of hexachloro-ethane with conversion of zerovalent into bivalent nickel, while the coordinated... 

Phosphorus pentachloride also reacts to yield arsenic trichloride.7 Arsenious oxide in aqueous solution is reduced by hypophosphorous acid, especially on boiling, when phosphine is liberated and brown arsenic precipitated.8 The reduction is readily brought about by calcium hypophosphite dissolved in 10 parts of hydrochloric acid (dens. 1-126), this salt being preferable in use to the sodium salt and providing an extremely sensitive reagent, although in the presence of slight traces of arsenic the brown colour may appear only after the lapse of 20 to 30 minutes.9 Arsenious oxide dissolves in arsenic trichloride to form an oxychloride.10... 

Protactinium pentachloride (42) and pentabromide (43) form both 1 1 and 1 2 complexes with phosphine oxides, the former being analogous to those formed by niobium, tantalum, and uranium pentahalides (26, 42, 43). Unlike niobium and tantalum pentachloride (42, 64) however, they do not react with excess triphenylphosphine oxide (TPPO) to form... 

---