Organometallic and organometalloidal fluorine compounds. Part XII. Bistrifluoromethylphosphinic acid and related phosphorus oxy-acids

Emeléus, H. J.; Haszeldine, R. N.; Paul, Ram Chand

doi:10.1039/jr9550000563

Cited by 45 publications

(26 citation statements)

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“…www.eurjic.orgSalt 7 is stable in dme or CH 3 CN solutions, as well as in the solid state for months at 20°C, but it is extremely sensitive to moisture. Also, storing the solid especially in glassware causes decomposition into bis(trifluoromethyl)phosphinic (8) [6,14] and (trifluoromethyl)phosphonic (10) [6,15] acids (Scheme 6).…”

Section: P(o) With Me 3 Sicf 3 and Csfmentioning

confidence: 99%

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

et al. 2007

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The unique pseudo‐trigonal‐bipyramidal CF3PF3O– and (CF3)2PF2O– anions were obtained and characterised for the first time. They were formed by the reactions of (PhO)3P(O), Me3SiCF3 and the fluoride ion sources [Me4N]F and CsF, respectively, in glyme. These anions represent the stable transition states postulated for nucleophilic substitution at a tetrahedral phosphorus atom. The salt Cs[(CF3)2PF2O] (7) is stable at room temperature for a month, while [Me4N][CF3PF3O] (1) dismutates into [Me4N][CF3PF(O)O] (2) and [Me4N][CF3PF5] (3) above 0 °C. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Section: P(o) With Me 3 Sicf 3 and Csfmentioning

confidence: 99%

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

et al. 2007

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“…(c) With Tris(trifl~ioromethyl)phosphorus Diflrroride Trimethyl(trifluoromethy1)tin (2.70 g, 11.6 mmoles) and (CF3)3PF2 (1.86 g, 6.75 mmoles) were kept at 25' for 6 h, by which time a small amount of white solid had appeared. Fractionation gave unreacted tin compound (2.40 g, 10.4 mmoles) and phosphorane (1.56 g, 5.66 mmoles) as the only volatile products.…”

Section: Adducts Ofmentioning

confidence: 99%

“…On heating, it did not melt or (b) With Bis(trifiorotnetIgvI)phosphorrrs Trifluoride Trimethyl(trifluoromethy1)tin (1. 90 g, 8.15 mmoles) and (CF3),PF3 (1.50 g, 6.63 mmoles) were kept in a sealed tube at 25' for 6 h, by which time a grey solid had formed. Fractionation gave unreacted tin compound (0.34 g, 1.46 mmoles) as the only volatile product, indicating that 6.69 mmoles of it remained in the solid adduct for a reacting ratio of 111.0.…”

Section: Adducts Ofmentioning

confidence: 99%

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Trifluoromethyl-substituted fluorophosphates and fluoroarsenates

Chan¹,

Willis²

1968

Can. J. Chem.

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Synthetic routes have been developed to salts containing the anions [CF3PF5]−, [(CF3)2PF4]−, [(CF3)3PF3]−, [(CF3)2AsF4]−, and [(CF3)3AsF3]−. These are isolated as stable solids with Cs+, or sometimes Ag+, as the cation. Their 19F n.m.r. spectra are discussed, and it is suggested that the bis- and tris-(trifluoromethyl)-substituted fluorophosphates have a trans configuration.Trimethyltrifluoromethyltin, (CH3)3SnCF3, forms 1:1 complexes with PF5, (CF3)2PF3, and (CF3)3PF2. It is suggested that transfer of a trifluoromethyl group as CF3− has occurred here, leading to the formation of trimethyltin derivatives of the trifluoromethyl-substituted fluorophosphates.

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“…Whereas hydrolysis of triaryldichlorophosphoranes yields phosplline oxides (1 0) , hydrolysis of tristrifluoromethyldichlorophosphorane (11) gives bistrifluorometlz~~lphosphinic acid and one equivalent of fluoroform.…”

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confidence: 99%

Chemistry of the Trifluoromethyl Group: Part Iii. Phenylbistrifluoromethylphosphine and Related Compounds

Beg¹,

Clark²

1961

Can. J. Chem.

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PART 111. PHENYLBISTRIFLUOROMETHYLPHOSPHINE AND RELATED COMPOUNDS1 ABSTRACT 'I'he reaction of trifluoroiodomethane with tetraphenylcyclotetraphosphine leads to the rormation of ~henvlbistrifluoromethvl~hos~hine and ~he~lvltrifluoromethvliodo~hos~hine. The mechanism of t h e reaction is discusseh and the physfcal and chemical prbpert'ies of these compounds itre reported. Bromine reacts with phenylbistrifluoromethylphosphine to form phenylbistrifluoron~ethyldibromophosphorane which is hydrolyzed to phenyltrifluoromethylphosphinic acicl, CGH~(CF~)P(O)OH. INTRODUC'I'IONIn previous papers in this series, the donor properties of methyl-trifluorometh ylphosphines were studied by the investigation of their ability , t o form complexes with boron trifluoride and platinuin (11) chloride ( I ) , and with a series of nickel (11) salts (2). Since much is known of the corresponding coinplexes of aryl phosphines, it seemed worthwhile to study the donor properties of aryl-trifluoron~ethyl-phosphines. Unlike the inethyl-trifluoroitiethyl-phosphines which have been known for some time (3, 4, 5), the phenyl-trifluoromethyl-phosphines had not been previously reported, although their arsine a~ialogues had been prepared (6). We now report the preparation of phenylbistrifluoroniethylphosphine. DISCUSSION AND RESULTSPhe~~ylbistrifluoron~etl~ylphosphiiie has been prepared by the reaction of trifluoroiodomethane with tetraphe~~ylcyclotetraphospl~i~~e, the properties of which have been reported by other workers (7,8,9). The reaction was performed a t 185', above the melting point of the tetraphosphine, and the other reaction products, besides phenylbistrifluoronlethylphosphine, are phenyltrifluorometl~yliodophosphine, which is a very illvolatile reddish brown liquid, and small amounts of fluoroform and hexafluoroethane.The mechanism of this reaction, involving the interaction of a perfluoroiodoalkane with a four-membered phosphorus ring is of some interest. R free-radical mechanism involving fission of phosphorus-phosphorus bonds by the attack of CFS radicals seems probable. This is supported by the fact that the reaction will occur thermally or on ultraviolet irradiation of the tetraphosphine with trifluoroiodomethane. Since the simultaneous breaking of four P-P l~o n d s is unlikely, the following reaction scheme inay be suggested. For personal use only.

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Organometallic and organometalloidal fluorine compounds. Part XII. Bistrifluoromethylphosphinic acid and related phosphorus oxy-acids

Cited by 45 publications

References 0 publications

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

Trifluoromethyl-substituted fluorophosphates and fluoroarsenates

Chemistry of the Trifluoromethyl Group: Part Iii. Phenylbistrifluoromethylphosphine and Related Compounds

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