Phosphorus trifluoride complexes

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. ... 

The block copolymer of ethylene oxide and 3,3-dimethylthietane shows useful properties of complexing halogen and heavy metal salts (79MI51402). Thietanes can be polymerized with methylmagnesium iodide as well as with a variety of electrophiles such as methyl sulfate, trimethyloxonium tetrafluoroborate, triethylaluminum, boron trifluoride and phosphorus trifluoride (67IC1461, 67MI51400). Thietane (210) has been patented as a stabilizer for poly(vinyl chloride) (73USP3767615). 

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). 

In our study of the fluorination of coordinated chlorophosphine ligands (23), we started out with tetrakis(trichlorophosphine)nickel-(0), which could previously be converted into tetrakis(trifluorophosphine)nickel-(0) by displacement of the coordinated phosphorus trichloride with excess phosphorus trifluoride in a sealed tube (32). The limitations of this method, requiring the use of phosphorus trifluoride, a low boiling gas, under pressure, and involving the mechanical separation of the fluorophosphine complex from phosphorus trichloride, are obvious, and the yield was low. A straightforward method for the synthesis of this interesting compound was found in the fluorination of the coordinated phosphorus trichloride with potassium fluorosulfinate ... 

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. 

FjO ReSC6, Rhenium(I), pentacarbonyl-(trifluoromethanesulfonato)-, 26 115 FjP, Phosphorus trifluoride, 26 12 F4AuiBOP,C54H45, Gold(l +), p,-oxo-[tris[(triphenylphosphine)-tetrafluoroborate(l -), 26 326 F4B, Borate(l-), tetrafluoro-molybdenum and tungsten complexes, 26 96-105... 

Tertiary phosphine analogs have been prepared from [Rh(NO)2Cl]x.1301 Nitrosyltris(phosphorus trifluoride)rhodium has been prepared from both rhodium(—I) and rhodium(I) complexes (equations 294-296).1297 Their physical properties are listed in Table 90. The triphenylphosphine complex is quite reactive (Scheme 42). Both electronic1312 and 31P NMR spectrometry show the equilibrium constant for the reaction (297) to be of the order of 10-4moldm3 in dichloromethane, benzene1312,1313 or THF,1313 so the reactivity of the complex cannot arise from the facile loss of a... 

Phosphorus trifluoride is a colorless gas, best made by fluorination of PC13 with AsF3 or ZnF2. It forms complexes with transition metals similar to those formed by carbon monoxide. Like CO, it is highly poisonous because of the formation of a hemoglobin complex. Unlike the other trihalides, PF3 is hydrolyzed only slowly by water, but it is attacked by alkalis. 

The Nature of the Coordinate Link. Part IV. Complex Formation by Phosphorus Trifluoride , J. Chatt and A. A. Williams, J. Chem. Soc., 1951, 3061. 

The B resonance spectra have been used to follow the deuteration of tetraborane by fully deuterated diborane. The spectra of the two deuterated tetraboranes B4H8D2 and B4D8H2 have been discussed it was reported that the former compound quickly reverted to normal tetraborane. The spectra of the two complexes of tetraborane with carbon monoxide and phosphorus trifluoride were described by the same authors. The B spectrum confirmed the structure of the g-deuterotetraborane-10 with a bridging deuterium atom. ° ... 

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