Phosphorus trifluoride

Phosphorus trifluoride is a ligand that is used extensively in coordination chemistry. It substitutes readily into various metal carbonyl complexes using either thermal or photochemical techniques. As a ligand, it is unique in its similarity to carbon monoxide in lower-valent organometallic compounds. In its role as a model for CO, a number of studies are possible that cannot be done on the carbonyls themselves.1 The name normally used for PF3 in complexes is trifluorophosphine. 

Our resolution to this dilemma has been to work out a compact procedure based upon the fluorinating agent SbF3 catalyzed by SbCl5 using acetonitrile as a solvent (i.e., the Swarts reaction).6 

Owing to the toxicity of PF3, this reaction should be carried out in a well-ventilated hood. 

If the PF3 is not to be used immediately, it can be condensed into a metal-pressure vessel at liquid nitrogen temperature using vaccum techniques. 

The — 78 °C trap and molecular sieve trap are designed to remove CH3CN. Since traces of moisture are inevitably present, this means that HC1 is also likely to be produced the molecular sieve trap will also remove it. An alternate 

Oil-Alled bubblers are placed at the start of the gas train and after the PFj condenser to monitor the gas flow. About 300 mL of acetonitrile, from a fresh bottle with a water content of no more than 0.05%, is admitted to the flask. The acetonitrile can be dried over 3A molecular sieves. As purge gas, heUum is preferred but nitrogen can also be used. Under a gas purge, 150 g (0.84 mol) of SbFj is dropped in over a period of a few minutes with vigorous stirring. If the order of addition is reversed, the SbFj tends to form clumps and resists stirring. Three milliters of (0.02 mol) SbCIs is added. The cold Anger is cooled 

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Phosphorus trifluoride is a colourless gas the molecule has a shape similar to that of phosphine. Although it would not be expected to be an electron donor at all (since the electronegative... 

Stereochemical studies of metal carbonyl-phosphorus trifluoride complexes. R. J. Clark and M. A, Busch, Acc. Chem. Res., 1973, 6,246-252 (34). 

A comprehensive review of the preparation, reactions, and n.m.r. spectra of phosphorus-fluorine compounds has appeared. This year s literature has been notable for the first detailed applications of ab initio SCF-MO calculations to the problems of bonding in halogenophosphines and their derivatives. - Comparison of the results of such theoretical calculations with experimental data obtained from photoelectron spectra shows a good correlation in the case of phosphorus trichloride and phosphoryl chloride, and of phosphorus trifluoride and its borane complex. ... 

Phosphorus pentafluoride Phosphorus trifluoride F T Steel, nickel, Monel and Pyrex for dry gas. For moist gas hard rubber and paraffin wax Steel, nickel, Monel and the more noble metals and Pyrex for dry gas... 

Chromyl chloride at high concentration ignites in fluorine, while phosphorus penta-chloride, phosphorus trichloride and phosphorus trifluoride ignite on contact [1]. Boron trichloride ignites in cold fluorine, and silicon tetrachloride on warming [2],... 

Dimethylamino)difluorophosphine has been prepared directly from phosphorus trifluoride and dimethylamine5,6 and also by the action of dimethylamine on (triehloromethyl)difluorophos-phine.13 The most convenient procedure yet reported4 appears to be the fluorination of C12PN(CH3)2 using ant mony trifluoride or sodium fluoride as a fluorinating agent. 

Phosphorus trifluoride has been used as a reactant gas in calorimetry to act as a fluorine acceptor rather than donor. The heats of formation of xenon fluorides have been calculated from the reaction heats (137) ... 

Phosphorus azide difluoride, 4315 Phosphorus trifluoride, 4339 Phosphorus triiodide, 4636 Tetrachlorodiphosphane, 4171 Tetraiododiphosphane, 4637... 

Reaction with phosphorus trichloride yields phosphorus trifluoride and with phosphoryl fluoride and sulfur trioxide, the product is phosphorus penta-fluoride ... 

Treating phosphorus trifluoride with bromine and then heating the product phosphorus trifluoride dibromide, PFsBr2 ... 

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