Cyclic phosphines and arsines. IV. Perfluoroalkyl-substituted cyclic phosphines

Ang, H. G.; Redwood, M. E.; West, BO

doi:10.1071/ch9720493

Cited by 15 publications

(10 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…After removal of excess HCl, the resulting colourless liquid was identified as (C 2 F 5 ) 2 PCl by multi-nuclear NMR [18] and IR spectroscopy. [12] Scheme 1. Reaction pathways for the syntheses of bis(pentafluoroethyl)phosphane derivatives (C 2 F 5 ) 2 PX (X = H, F, Cl, Br, OH).…”

Section: Preparation Of Bis(pentafluoroethyl)phosphane Derivativesmentioning

confidence: 99%

“…[11] Treating the iodo compounds with silver or mercury chloride furnishes the corresponding chloro derivatives. [12] Recently published, significantly improved syntheses of (C 2 F 5 ) 2 PCl [4] and (C 2 F 5 ) 2 POH [13] start from the technical product (C 2 F 5 ) 3 PF 2 and proceed via P(C 2 F 5 ) 3 and (C 2 F 5 ) 2 PO -salts as intermediates, respectively. The improved protocol for the synthesis of (C 2 F 5 ) 2 POH has allowed the preparation of several stable and catalytically active transition-metal complexes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

et al. 2013

View full text Add to dashboard Cite

(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.

show abstract

Section: Preparation Of Bis(pentafluoroethyl)phosphane Derivativesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2013

View full text Add to dashboard Cite

show abstract

“…The first synthesis of (C 2 F 5 ) 2 PCl originates from 1972 when Ang et al successfully reacted (C 2 F 5 ) 2 PI with AgCl. [12] After 15 days, they obtained the product in 93 % yield.…”

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

View full text Add to dashboard Cite

(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°.

show abstract

“…[9,10] The first phosphorus compounds bearing C 2 F 5 groups were synthesized analogously to the synthesis of the CF 3 derivatives by the high-pressure reaction of C 2 F 5 Ia nd elemental phosphorus. [11,12] Iodine/chlorine exchange was achievedb yt reatment with AgCl [11] or SbCl 3 . [13] Combination of C 2 F 5 PI 2 with SbF 3 led to the formation of the corresponding fluoro compound [14] whereas C 2 F 5 PBr 2 is still unknown.…”

Section: Introductionmentioning

confidence: 99%

Functionalized Pentafluoroethylphosphanes

Allefeld

Neumann

Stammler

et al. 2015

Chemistry A European J

View full text Add to dashboard Cite

Bis(diethylamino)pentafluoroethylphosphane represents a versatile starting material for the synthesis of functionalized pentafluoroethylphosphanes. Perfluoroalkyl substituted aminophosphanes themselves already exhibit interesting coordination properties and were treated with the catalytically relevant salts PtCl2 and PdCl2 affording trans-[Cl2M{P(C2F5)(NEt2)2}2]. The hitherto unknown (C2F5)PBr2, accessible in good yields by treatment of C2F5P(NEt2)2 with HBr, was smoothly transformed into the corresponding phosphane, C2F5PH2, or fluoro derivative, C2F5PF2. Acidic hydrolysis of C2F5 P(NEt2)2 yielded the phosphinic acid C2F5P(O)(OH)H, the anion of which was structurally characterized. The phosphinic acid smoothly adds to the carbonyl group of acetone under P-C bond formation. An analogous reaction with aldehydes, for example, salicyl aldehyde, offers the possibility to generate stereocenters.

show abstract

Cyclic phosphines and arsines. IV. Perfluoroalkyl-substituted cyclic phosphines

Cited by 15 publications

References 0 publications

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

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

Functionalized Pentafluoroethylphosphanes

Contact Info

Product

Resources

About