Solid nickel phosphorus compounds

V.6.2 Phosphorus compounds and complexes V.6.2.1 Solid nickel phosphorus compounds... 

The catalyst was subjected to chemical anal3rsis, dissolution in a dilute solution of hydrochloric acid. X-ray diffraction analysis, and DTA. Inspection of these analytical data leads to the conclusion that the main constituent of this catalyst is an amorphous solid solution composed of metallic nickel and the nickel-phosphorus compound of formula Nii.gP, the overall composition of which is NirNii.sP = 2.7 1. 

Both compounds being colorless and volatile, the liquid methyl derivative could be distilled in vacuo (b.p. 66-68° at 3.5 mm.), while the phenyl compound is a crystalline solid melting at 66°, which is sublimable in vacuo. The fluorination reactions occur somewhat less vigorously than in the case of the phosphorus trichloride nickel-(0) complex, and gentle heating was normally required to initiate the reaction. Benzene was used as a solvent. 

Hydrated nickel(II) salts in the presence of the ligand p3 react with both white phosphorus and yellow arsenic, breaking up the structure of the tetraatomic P4 and As4 molecules to form triatomic cyclo-triphosphorus and cyc/o-triarsenic species. These fragments act as trihapto ligands yielding double sandwich complexes (equation 99).292 The compounds are air-stable both in the solid state and in solution. Upon reduction with NaBH the complexes of equation... 

Other elements with which nickel forms binary compounds, especially at higher temperature, are. boron, carbon, nitrogen, silicon, and phosphorus. Like NiO. these compounds may depart slightly or even considerably from daltonide composition, frequently being interstitial compounds, and with higher elements of transition groups 5 and 6, merging into the interstitial compound-solid solution picture which nickel exhibits with the other transition metals. 

Tetrakis[phosphorus(III) chloride] nickel is a pale yellow crystalline solid at room temperature and becomes colorless on cooling to about — 30°. This compound is stable in air when dry and unreactive with water at room temperature for a period of several days. It reacts slowly in the cold with dilute acids and with concentrated sulfuric or hydrochloric acid, but reacts rapidly in hot acid solutions. The compound reacts rapidly with ammonium hydroxide but more slowly with sodium hydroxide.1 It is reported that no decomposition occurs below 120° when the solid is heated, but that at higher temperatures the solid is decomposed and phosphorus (III) chloride is liberated 1 however, decomposition at 80° has been observed. Tetrakis[phos-phorus(III) chloride] nickel appears to be nonvolatile. 

BENSULFOID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry materia forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysis, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium iodate, potassium peroxoferrate, rubidium acetylide, ruthenium tetraoxide, sodium, sodium chlorite, sodium peroxide, tin, uranium, zinc, zinc(II) nitrate, hexahydrate. Forms heat-, friction-, impact-, and shock-sensitive explosive or pyrophoric mixtures with ammonia, ammonium nitrate, barium bromate, bromates, calcium carbide, charcoal, hydrocarbons, iodates, iodine pentafluoride, iodine penloxide, iron, lead chromate, mercurous oxide, mercury nitrate, mercury oxide, nitryl fluoride, nitrogen dioxide, inorganic perchlorates, potassium bromate, potassium nitride, potassium perchlorate, silver nitrate, sodium hydride, sulfur dichloride. Incompatible with barium carbide, calcium, calcium carbide, calcium phosphide, chromates, chromic acid, chromic... 

SULFUR or SULFUR, MOLTEN or SULFUR, SOLID (7704-34-9) Combustible solid (flash point 405°F/207°C). Finely divided dry material forms explosive mixture with air. The vapor reacts violently with lithium carbide. Reacts violently with many substances, including strong oxidizers, aluminum powders, boron, bromine pentafluoride, bromine trifluoride, calcium hypochlorite, carbides, cesium, chlorates, chlorine dioxide, chlorine trifluoride, chromic acid, chromyl chloride, dichlorine oxide, diethylzinc, fluorine, halogen compounds, hexalithium disilicide, lampblack, lead chlorite, lead dioxide, lithium, powdered nickel, nickel catalysts, red phosphorus, phosphorus trioxide, potassium, potassium chlorite, potassium... 

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