The synthesis of tris(perfluoroalkyl)phosphines

Murphy-Jolly, Makeba B.; Lewis, Lesley C.; Caffyn, Andrew J. M.

doi:10.1039/b507752d

Cited by 61 publications

(55 citation statements)

References 36 publications

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“…[17] An efficient synthesis of (C 2 F 5 ) 2 POH starts from (C 2 F 5 ) 3 PF 2 , which is currently produced on a multikilogram scale by the Merck Company (Darmstadt, Germany) by the electrochemical fluorination of triethylphosphane in anhydrous hydrogen fluoride. [18,19] The treatment of (C 2 F 5 ) 3 PF 2 with aqueous HF yields the strong acid [20] which hydrolyzes at 130 8C with formation of bis(pentafluoroethyl)-phosphinic acid (C 2 F 5 ) 2 P(O)OH.…”

Section: Resultsmentioning

confidence: 99%

The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH

Hoge¹,

Bader²,

Beckers³

et al. 2009

Chemistry A European J

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The industrial product (C(2)F(5))(3)PF(2) is transformed into the phosphinic acid chloride (C(2)F(5))(2)P(O)Cl, which reacts with an excess of Bu(3)SnH in a clean, multistep reaction to give the stannyl derivative (C(2)F(5))(2)POSnBu(3). Subsequent treatment with gaseous HBr leads to the formation of (C(2)F(5))(2)POH, which is isolated in 70 % yield. Besides (CF(3))(2)POH, bis(pentafluoroethyl)phosphinous acid, (C(2)F(5))(2)POH, represents the second known example of a phosphinous acid that is predicted by using density functional theory calculations at the B3PW91/6-311G(3d,p) level to be more stable than the phosphane oxide tautomer, the energy difference being 11.7 kJ mol(-1). Only the phosphinous acid isomer is detectable in the gas phase and in solution. However, investigations of the neat liquid reveal a temperature-dependent tautomeric equilibrium with the phosphane oxide isomer (C(2)F(5))(2)P(O)H, which is characterized by vibrational and multinuclear NMR spectroscopic methods in combination with quantum-chemical calculations.

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Section: Resultsmentioning

confidence: 99%

The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH

Hoge¹,

Bader²,

Beckers³

et al. 2009

Chemistry A European J

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“…[6,9] The C 2 F 5 group can also be introduced by the fluoride-mediated reaction of C 2 F 5 SiMe 3 with (PhO) 2 -PC 2 H 4 P(OPh) 2 . [10] The reaction of white phosphorus with C 2 F 5 I under high pressure and temperatures is not a favourable alternative to the synthesis of bis(pentafluoroethyl)phosphane derivatives. Mono-and bis(pentafluoroethyl)iodophosphane were obtained in this way only in very low yields.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Bis(pentafluoroethyl)phosphanes: Improved Syntheses and Molecular Structures in the Gas Phase

et al. 2013

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(C2F5)2PNEt2 represents an excellent starting material for the selective synthesis of bis(pentafluoroethyl)phosphane derivatives. The moderately air‐sensitive aminophosphane is accessible on a multi‐gram scale by treating Cl2PNEt2 with C2F5Li. Treatment with gaseous HCl or HBr yielded the corresponding phosphane halides (C2F5)2PCl and the so far unknown (C2F5)2PBr in good yields. The hitherto unknown (C2F5)2PF was obtained by treating (C2F5)2PBr with excess antimony trifluoride. Treatment of (C2F5)2PCl with Bu3SnH led to the quantitative formation of (C2F5)2PH. Deprotonation formally yielded the (C2F5)2P– anion in a form that was stabilized by coordination to mercury ions to form the complex [Hg{P(C2F5)2}2(dppe)]. An improved high‐yielding synthesis of (C2F5)2POH was achieved by treating (C2F5)2PNEt2 with p‐toluenesulfonic acid. The gas‐phase structures of (C2F5)2PH and (C2F5)2POH were determined by electron diffraction. The vibrational corrections employed in the data analysis of the diffraction data were derived from molecular dynamics calculations. Both compounds exist in the gas phase mostly as C1‐symmetric cis,cis conformers with regard the orientation of the C2F5 groups relative to the functional groups H and OH. The presence of a second conformer at ambient temperature is likely in both cases. The refined amounts of dominant conformers are 94(6) and 85(6) % for (C2F5)2PH and (C2F5)2POH, respectively. The conformational behaviour was further explored by potential energy surface scans based on DFT calculations. Important experimental structural parameters for the most stable conformers are re(P–C)average = 1.884(3) Å for (C2F5)2PH and re(P–C)average = 1.894(4) Å and re(P–O) = 1.582(3) Å for (C2F5)2POH. The different coordination properties of (C2F5)3P, (C2F5)2POH, (CF3)3P and (CF3)2POH were evaluated by complex formation with [Ni(CO)4]: the maximum achievable number of CO ligands substituted by (C2F5)3P is 1, by (C2F5)2POH is 2, by (CF3)3P is 3 and by the smallest ligand (CF3)2POH is 4.

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“…A safe and more efficient route to (CF 3 ) 2 PC 2 H 4 PA C H T U N G T R E N N U N G (CF 3 ) 2 and (C 2 F 5 ) 2 PC 2 H 4 PA C H T U N G T R E N N U N G (C 2 F 5 ) 2 has subsequently been found in the transformation of (PhO) 2 PCH 2 CH 2 PA C H T U N G T R E N N U N G (OPh) 2 with Me 3 SiCF 3 and Me 3 SiC 2 F 5 , respectively. [8] Abstract: A C H T U N G T R E N N U N G (C 2 F 5 ) 2 PCl is now accessible through a significantly improved synthesis protocol starting from the technical product (C 2 F 5 ) 3 PF 2 . (C 2 F 5 ) 3 PF 2 was reduced in the first step with NaBH 4 in a solvent-free reaction at 120 8C.…”

Section: Introductionmentioning

confidence: 99%

Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

Hayes

Berger

Mitzel

et al. 2011

Chemistry A European J

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(C(2)F(5))(2)PCl is now accessible through a significantly improved synthesis protocol starting from the technical product (C(2)F(5))(3)PF(2). (C(2)F(5))(3)PF(2) was reduced in the first step with NaBH(4) in a solvent-free reaction at 120 °C. The product, P(C(2)F(5))(3), was treated with an excess of an aqueous sodium hydroxide solution to afford the corresponding phosphinite salt Na(+)(C(2)F(5))(2)PO(-) selectively under liberation of pentafluoroethane. Subsequent chlorination with PhPCl(4) resulted in the selective formation of (C(2)F(5))(2)PCl, which was isolated by fractional condensation in an overall yield of 66 %. The gas electron diffraction (GED) pattern for (C(2)F(5))(2)PCl was recorded and found to be described by a two-conformer model. A quantum chemical investigation of the potential-energy surface revealed the possible existence of many low-energy conformers, each with a number of low-frequency vibrational modes and therefore large-amplitude motions. The conformer calculated to be most stable was also found to be most abundant by GED and comprised 61(5) % of the total. The molecular structure parameters determined by GED were in good agreement with those calculated at the MP2/TZVPP level of theory; the only significant difference was a discrepancy of about 3° in the C-P-C angle, which, for the lowest-energy conformer, was refined to 98.2(4)° and was calculated to be 94.9°.

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The synthesis of tris(perfluoroalkyl)phosphines

Abstract: Tris(perfluoroalkyl)phosphines, of interest as tunable alternatives to the carbon monoxide ligand, can be synthesised by the nucleophile mediated reaction of perfluoroalkyltrimethylsilanes with triphenylphosphite; the method can be extended to diphosphines.

Cited by 61 publications

References 36 publications

The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH

The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH

Functionalized Bis(pentafluoroethyl)phosphanes: Improved Syntheses and Molecular Structures in the Gas Phase

Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

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The synthesis of tris(perfluoroalkyl)phosphines

Abstract: Tris(perfluoroalkyl)phosphines, of interest as tunable alternatives to the carbon monoxide ligand, can be synthesised by the nucleophile mediated reaction of perfluoroalkyltrimethylsilanes with triphenylphosphite; the method can be extended to diphosphines.

Cited by 61 publications

References 36 publications

The Bis(pentafluoroethyl)phosphinous Acid (C2F5)2POH

The Bis(pentafluoroethyl)phosphinous Acid (C2F5)2POH

Functionalized Bis(pentafluoroethyl)phosphanes: Improved Syntheses and Molecular Structures in the Gas Phase

Chlorobis(pentafluoroethyl)phosphane: Improved Synthesis and Molecular Structure in the Gas Phase

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The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH

The Bis(pentafluoroethyl)phosphinous Acid (C₂F₅)₂POH