Potassium fluorosulfinate

Evidence for the existence of this type of compound appeared only in 1967. Seel, Gombler, and Budenz 145) reacted trihalomethanesulfenyl chlorides with active potassium fluoride (prepared through degradation of potassium fluorosulfinate) at 150°C in the gas phase ... 

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 ... 

Using the potassium fluorosulfinate method further fluorophosphine-nickel-(O) complexes could be prepared (23), according to ... 

The preparation of tetrakis(trifluorophosphine)nickel-(0), tetrakis (methyl-difluorophosphine) nickel- (0), and tetrakis (phenyldifluorophosphine) nickel- (0) from the corresponding chloro compounds, using potassium fluorosulfinate as a fluorinating agent, has been described (23). 

Not yet obtained in satisfactory purity prepared by metathetical reaction from (PCls)s-Mo(CO)a (2) with potassium fluorosulfinate. In addition to carbonyl absorptions, infrared spectrum exhibits only strong P—F stretching absorptions at 852 cm. -1 (m), 867 cm,-1 (vs), and 880 cm. (sh), in the region for phosphorus trifluoride (10),... 

The author acknowledges the encouragement of F. Seel, who directed his attention to the study of potassium fluorosulfinate in phosphorus-fluorine chemistry. 

Fluorophosphinenickel(O) complexes can be formed by reaction of the corresponding chloro-phosphine complexes with potassium fluorosulfinate (equations 9 and 10).1718 The metal inhibits oxidation of the ligand to the phosphinic fluoride, a reaction that occurs readily to the free ligand. 

Ni(PF3)4 can act as a source of PF3 in reactions with metal carbonyl complexes (method F), and fluorination of preformed carbonyl metal-PCl3 complexes using potassium fluorosulfinate has also been described (method G). 

Potassium fluorosulfinate, KSO2F, reacts with alkyl- or aryldichloro-phosphines to form phosphonic acid fluorides RPOF2 and phosphono-thioic acid fluorides RPSF2 rather than the desired difluorophosphine... 

Seel and co-workers (296-298) have obtained methyldifiuorophos-phine and dimethylfluorophosphine by reacting the vapor of the corresponding chlorophosphine with active potassium fluoride formed by pyrolysis of potassium fluorosulfinate in vacuo. 

The main synthetic route to these compounds is via fluorination of the corresponding chlorophosphite usually with SbFg 136, 284, 201, 202, 260, 304), AsFg 136), NaF 284), or potassium fluorosulfinate 284, 295). 

Exchange of chlorine by fluorine can be easily effected by reacting the chlorophosphine-metal complex with antimony trifluoride (250), arsenic trifluoride (281), zinc fluoride (281), potassium fluorosulfinate (281, 284, 295), or potassium fluoride in tetramethylene sulfone (250). For example,... 

Powdered trimeric or tetrameric phosphonitrilic chloride is reacted with potassium fluorosulfinate at 120 to 150°C. The degree of polsunerization is not altered by the reaction. 

Potassium fluorosulfinate Carboxylic acid fluorides from carboxylic acid chlorides... 

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