Organometallic and organometalloidal fluorine compounds. Part X. Trifluoromethyl-phosphonous and -phosphonic acids

Bennett, F. W.; Emeléus, H. J.; Haszeldine, R. N.

doi:10.1039/jr9540003598

Cited by 37 publications

(17 citation statements)

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“…In a forthcoming experiment, he was able to use this reaction for a preparative synthesis of bis(trifluoromethyl)phosphinic acid, (CF 3 ) 2 P(O)OH. (4) Bis(trifluoromethy)phosphinic acid is unstable in the presence of water and yields in a selective reaction trifluoromethylphosphonic acid, CF 3 P(O)(OH) 2 , and fluoroform. [4].…”

Section: Resultsmentioning

confidence: 99%

“…(4) Bis(trifluoromethy)phosphinic acid is unstable in the presence of water and yields in a selective reaction trifluoromethylphosphonic acid, CF 3 P(O)(OH) 2 , and fluoroform. [4]. This reaction is established as a method for the identification of bis(trifluoromethyl)phosphinic acid because the amount of evolved fluoroform corresponds with the amount of bis(trifluoromethyl)phosphinic acid [3].…”

Section: Resultsmentioning

confidence: 99%

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Synthesis and Structure of [Hg{OP(O)CF3(OH)}2(PMe3)3], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric ChainsDedicated to Professor Dieter Naumann on the Occasion of his 60th Birthday

Pantenburg

Thösen

Hoge

2002

Z. anorg. allg. Chem.

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The hydrolysis of [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] yields colourless crystals of [Hg{OP(O)CF 3 (OH)} 2 (PMe 3 ) 3 ]. The proposed multistep reaction proceeds via primary hydrolysis of the starting material giving HgO and HP(CF 3 ) 2 . The latter is directly oxidized by HgO to (CF 3 ) 2 P(O)OH. The bis(trifluoromethyl)phosphinic acid hydrolyses to CF 3 P(O)(OH) 2 which reacts with [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] in the presence of PMe 3 to the title compound. The crystal structure was determined by X-ray single-crystal analysis (triclinic; P1; a ϭ 860.7(1), b ϭ 1007.6(2), c ϭ 1625.0(3) pm; α ϭ 96.09 (2), β ϭ 101.09 (2), γ ϭ 107.79(2)°; Z ϭ 2) Synthese und Struktur von [Hg{OP(O)CF 3 (OH)} 2 (PMe 3 ) 3 ], ein verzerrt trigonalbipyramidaler Komplex, der über Wasserstoff-Brücken zu polymeren Ketten verknüpft istInhaltsübersicht. Bei der Hydrolyse von [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] werden farblose Kristalle der Verbindung [Hg{OP(O)CF 3 (OH)} 2 (PMe 3 ) 3 ] erhalten. Der vorgeschlagene Reaktionsmechanismus der Hydrolyse verläuft über die intermediäre Bildung von HgO and HP(CF 3 ) 2 . Letzteres wird durch HgO zu (CF 3 ) 2 P(O)OH oxidiert. Die entstehende Bis(trifluormethyl)phosphinsäure hydrolysiert zu CF 3 P(O)(OH) 2 , welches in der Gegenwart von PMe 3 mit [Hg{P(CF 3 ) 2 } 2 (PMe 3 ) 2 ] zur Titelverbindung reagiert. Die Einkristall-Struktur-Analyse (triklin; P1; a ϭ 860.7(1),

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Synthesis and Structure of [Hg{OP(O)CF3(OH)}2(PMe3)3], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric ChainsDedicated to Professor Dieter Naumann on the Occasion of his 60th Birthday

Pantenburg

Thösen

Hoge

2002

Z. anorg. allg. Chem.

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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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“…This absorption occurs in the same region for the aryl and alkyl phosphinic acids RJ'(0)OI-I, which are weak acids. For the strong acid, trifluoron~ethylphosphonic acid, this vibration is shifted to the higher frequency of 1300 cin-' (13,14). This might suggest that phenyltrifluoromethylphosphinic acid is a fairly weak acid.…”

mentioning

confidence: 91%

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 X. Trifluoromethyl-phosphonous and -phosphonic acids

Cited by 37 publications

References 0 publications

Synthesis and Structure of [Hg{OP(O)CF3(OH)}2(PMe3)3], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric ChainsDedicated to Professor Dieter Naumann on the Occasion of his 60th Birthday

Synthesis and Structure of [Hg{OP(O)CF3(OH)}2(PMe3)3], a Distorted Trigonal Bipyramidal Complex Connected by Hydrogen Bridges to Polymeric ChainsDedicated to Professor Dieter Naumann on the Occasion of his 60th Birthday

New Anions of Pentacoordinate Phosphorus Containing Fluorine and Trifluoromethyl Groups

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

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