Phosphorus trifluoride, reaction + metal

Knowing all these facts, especially the difficult access to fluorophosphines and the poor donating abilities of phosphorus trifluoride (5, 6), we decided to use another approach, which readily led to a number of coordination compounds with fluorophosphine ligands—namely, the fluorination of chlorophosphines already coordinated to the transition metal, where the 3s electrons of phosphorus are blocked by the complex formation. There was no reaction between elemental nickel and phosphorus trifluoride, even under extreme conditions, whereas the exchange of carbon monoxide in nickel carbonyl upon interaction with phosphorus trifluoride proceeded very slowly and even after 100 hours interaction did not lead to a well defined product (5,6). 

The reaction between molybdenum hexacarbonyl and elemental fluorine at —65° results in the formation of Mo2F9, which upon thermal degradation produces molybdenum pentafluoride as one of the products.1 Other syntheses of molybdenum pentafluoride include the reduction of molybdenum hexafluoride with phosphorus trifluoride,2 tungsten hexacarbonyl, or molybdenum metal at high temperatures3 and the oxidation of powdered molybdenum metal with elemental fluorine at 900°.3 The present method consists in the reaction of molybdenum hexafluoride with powdered molybdenum metal at 60° and results in the formation of pure molybdenum pentafluoride in yields of 80% and greater. 

Recently, Kruck (118) succeeded in preparing Ni(PF3)4 from metallic nickel and phosphorus trifluoride under drastic conditions (350 atm., 100°C.), as did Street and Burg under mild conditions (181), even though Wilkinson and Chatt (52, 202) had previously reported that no reaction occurs between these reagents. 

Phosphorus tribromide stereochemistry, 36 Phosphorus trichloride metal complexes solvolysis, 418 stereochemistry, 36 Phosphorus trifluoride stereochemistry, 36 Phosphorus trihalides stereochemistry, 36 Phosphorus triiodidc stereochemistry, 36 Photoaquation solid state, 471 Photocalorimetry, 410 Photochemical reactions, 397 applications, 408 mechanisms, 385 solid state, 470 Photochromism, 409 Photolysis... 

The redistribution reaction in lead compounds is straightforward and there are no appreciable side reactions. It is normally carried out commercially in the liquid phase at substantially room temperature. However, a catalyst is required to effect the reaction with lead compounds. A number of catalysts have been patented, but the exact procedure as practiced commercially has never been revealed. Among the effective catalysts are activated alumina and other activated metal oxides, triethyllead chloride, triethyllead iodide, phosphorus trichloride, arsenic trichloride, bismuth trichloride, iron(III)chloride, zirconium(IV)-chloride, tin(IV)chloride, zinc chloride, zinc fluoride, mercury(II)chloride, boron trifluoride, aluminum chloride, aluminum bromide, dimethyl-aluminum chloride, and platinum(IV)chloride 43,70-72,79,80,97,117, 131,31s) A separate catalyst compound is not required for the exchange between R.jPb and R3PbX compounds however, this type of uncatalyzed exchange is rather slow. Again, the products are practically a random mixture. 

Such representative non-metal elements as boron, silicon, phosphorus, sulfur, arsenic, antimony, selenium and tellurium react with chlorine trifluoride at room temperature or on very slight warming to produce the corresponding fluorides. These reactions are generally vigorous and are accompanied by heat and light [96]. 

One of the many important differences between phosphorus and nitrogen chemistry is the relative strengths of their bonds to hydrogen. The relatively weak P—H bond means that this functionality can be added across a wide variety of unsaturated molecules (alkenes, alkynes, carbonyls) and hence this represents an excellent method for preparing tertiary phosphines. The addition of P 11 compounds to C=0 and C=N has been described in detail by Gilheany and Mitchell.2 The reaction can be catalyzed by base (potassium hydroxide, butyllithium), acid (HC1, carboxylic acids, sulfonic acids, boron trifluoride), free radical (uv, organic peroxides, AIBN) or metal (simple metal salts, late transition-metal complexes). In some circumstances no catalyst is required at all for P 11 additions to proceed.60... 

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