The reaction of secondary phosphines and di-1-adamantylphosphine oxide with trifluoroacetic anhydride and hexafluoroacetone (original) (raw)
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The chemistry of some trifluoromethyl-phosphines
1961
CHEMISTRY OF SOME TRIFLUOROMETHYL-PHOSPHINES One particular aspect of the chemistry of the trifluoromethyl group is its high electron-withdrawing power which reduces the donor properties of normally strong bases. This investigation has been concerned with the chemistry of some phosphines containing this group. For this purpose, substituted phosphines containing methyl or phenyl and trifluoromethyl groups have been prepared. For the study of their donor properties, a series of addition compounds with boron trifluoride, platinum(II) chloride and nickel(II) salts have been prepared. The reported methods for preparing the methyl-trifluoromethylphosphines do not produce a good yield; therefore, an attempt has been made towards a better understanding of the reactions. The phenyl-trifluoromethyl-phosphines have been prepared by reacting trifluoroiodomethane with a phosphorus compound containing a P-P bond. Thus, a reaction with tetraphenylcyclotetraphosphine gives phenylbistrifluoromethylphosphine and phenyltrifluoromethyliodophosphine, and reaction with tetraphenlydiphosphine gives diphenyltrifluoromethylphosphine. The latter has also been prepared by reaction of trifluoroiodomethane with either triphenylphosphine or diphenylchlorophosphine. These new phosphines are colorless liquids (except phenyltrifluoromethyliodophosphine which is reddish-brown) of high boiling point. They are stable in air and cannot be hydrolysed with acid or water, except the iodophosphine C(.H S CF 3 PI, which reacts with water to give phenyltrifluoromethylphosphinic acid, a new oxyacid. Phenylbistrifluoromethylphosphine can be hydrolysed with aqueous alkali to give fluoroform and phenylphosphonous acid. Diphenyltrifluoromethylphosphine, on the other hand, cannot be hydrolysed by aqueous alkali, but reacts slowly with alcoholic potassium hydroxide to give' fluoroform and diphenylphosphinic acid. The phosphines form a further series of new compounds by reaction with halogens. Phenylbistrifluoromethylphosphine reacts with iodine to form trifluoroiodomethane, but forms phenylbistrifluoromethyldibromophosphorane with bromine. This compound also gives phenyltrifluoromethylphosphinic acid on aqueous hydrolysis, as obtained in the case of phenyltrifluoromethyliodophosphine. Besides forming the dibromophosphorane, diphenyltrifluoromethylphosphine is the first trifluoromethyl-phosphine known to form a diiodophosphorane. It is interesting to note that diphenyltrifluoromethylphosphine is difficult to hydrolyse, whereas the phosphoranes can be hydrolysed easily, giving fluoroform and diphenylphosphinic acid. By reaction with methyl iodide, this phosphine also forms a new phosphonium compound, methyldiphenyltrifluoromethylphosphonium iodide which is readily hydrolysed by cold water with the loss of the trifluoromethyl group. In general, phosphines containing one trifluoromethyl group show similar properties to those of their parent compounds, trimethylphosphine and triphenylphosphine, while those containing two trifluoromethyl groups are very similar in their behaviour to tristrifluoromethylphosphine. The phosphines containing more than one CF 3 group do not form addition compounds with boron trifluoride. The phenyl-trifluoromethyl-phosphines form more stable complexes than the methyltrifluoromethyl-phosphines. The phosphines containing up to two trifluoromethyl groups form complexes with platinum(II) chloride. A complex with tristrifluoromethylphosphine could not be obtained. Except dimethyltrifluoromethylphosphine, which forms mainly a cis isomer, the other phosphines, CH a (CF 3) 2 P, C 6 H 5 (CF 3).,P, and (C 6 H 5) 2 CF 3 P form mainly trans isomers. The non-occurrence of the tristrifluoromethylphosphine complex and the production of mainly trans isomers of the above-mentioned phosphines has been interpreted in terms of steric phenomenon. The phosphines containing more than one CF S group do not form complexes with nickel(II) salts. The nitrate complexes of trimethylphosphine and dimethyltrifluoromethylphosphine are paramagnetic, while the dichloro, dibromo, diiodo, and dithiocyanato complexes are diamagnetic. A correlation of the various properties, for example boiling points and heats of vaporization, has shown that the trifluoromethyl substituted phosphines are not anomalous in the general family of phosphines. An attempt has also been made towards a study of the infrared spectra of the phosphines and their compounds, and towards a correlation with the spectra of other phosphorus compounds. Finally, an approximate estimate of the "electronegativities" of a wide range of substituted phosphines gives values which are in good agreement with the observed order of reactivities of the phosphines studied, and assists in correctly placing the trifluoromethylphosphines in such a range, of compounds. 6 5 3 2 6 5 2 3 non-occurrence of the tristrifluoromethylphosphine complex and the production of mainly trans isomers of the abovementioned phosphines has been interpreted in terms of steric phenomenon. (iv) The phosphines containing more than one CF_ group j do not form complexes with nickel(II) salts. The nitrato complexes of trimethylphosphine and dimethyltrifluoromethylphosphine are paramagnetic, while the dichloro, dibromo, diiodo, and dithiocyanato complexes are diamagnetic. A correlation of the various properties, for example boiling points and heats of vaporization, has shown that the trifluoromethyl substituted phosphines are not anomalous in the general family of phosphines. An attempt has also been made towards a study of the infra-red spectra of the phosphines and their compounds, and towards a correlation with the spectra of other phosphorus compounds. Finally, an approximate estimate of the "electronegativities" of a wide range of substituted phosphines gives values which are in good agreement with the observed order of reactivities of the phosphines studied, and assists in correctly placing the trifluoromethylphosphines in such a range of compounds.
Journal of the American Chemical Society, 1971
Several reactions of rhodium(I) complexes of 1,2,5,6,8-pentamethylenecyclodecane (allene pentamer, C i 5HZ,,) are described_ Reaction of the chloride C 1 ,H2,RhCl with (pentafluorophenyl)lithium in diethyl ether gives the yellow crystalline o-pentafluorophenyl derivative C,,H2,RhC6FS, apparently the first known example of a derivative with a transition metal-carbon o-bond where all of the other ligands are coordinated carbon-carbon double bonds. Reaction of C,,H2,RhC1 with sodium cyclopentadienide in tetrahydrofuran solution gives yellow waxy Cr ,H,cRhC,H, shown by its NMR spectrum to have a tetruhapto-1,2,5,6,8-pentamethylenecyclodecane ligand and a pe,ztnlzupro-cyclopentadienyl ligand. The predominant ion in the mass spectrum of C,,H,,RhC,H5 is CrSH2eRhf which is formed by loss of C,H, from the molecular ion. Reaction of Cr5Hz0RhCl with stannous chloride in diethyl ether gives yellow Ci ,H2,RhSnCl,.
Role of Phosphine Sterics in Strained Aminophosphine Chelate Formation
Inorganic Chemistry
All manipulations were carried out under purified N 2 using standard Schlenk and/or Glove-box techniques. Deuterated solvents were obtained from Sigma-Aldrich and Cambridge Isotopes Laboratories and were dried prior to use. All solvents were dried by distillation from appropriate drying agents and were S3 stored over 3 Å molecular sieves under an N 2 atmosphere prior to use. Paraformaldehyde, dimethylamine (2.0 M in MeOH), n-butyllithium (1.6 M in hexanes), 2-bromopyridine, 2-methylpyridine, and Me NCH CH 2 Cl•HCl were purchased from Sigma Aldrich and used without purification. LiAlH 4 was purchased from Sigma Aldrich and recrystallized from Et 2 O prior to use. Ph 2 PCl, i Pr 2 PCl, t Bu 2 PCl were purchased from Alfa Aesar or Strem Chemicals. K 2 PtCl 4 was purchased from Pressure Chemicals. Syntheses of [Pt 2 Me 4 (-SMe 2) 2 ], (cod)PtMe 2 , and (cod)PtCl 2 were performed according to literature procedures. 1 Modified procedures (Sections S.1.2 and S.1.3) were used to prepare known species L 1 , L 8 , 2, and 12. 2 1 H and 31 P NMR data obtained for these species is provided for comparison with other complexes in this study. Elemental analyses were performed by Analytical Services in the Department of Chemistry, The University of British Columbia. ESI-MS and EI-MS were recorded on Waters LCMS and Kratos MS-50 instruments, respectively. The observed isotope patterns were in agreement with calculated patterns in all cases, and the highest intensity signal is reported. The phosphine ligands prepared in this study were readily oxidized by air, and we were unable to obtain satisfactory elemental analyses for those ligands which exist as liquids at room temperature. NMR spectra were recorded on 300 or 400 MHz Bruker Avance NMR spectrometers. NMR experiments were performed at 23 °C and chemical shifts () are reported in ppm. The multiplicity of signals with 195 Pt satellites are reported as the multiplicity of the parent signal, with the presence of satellites is indicated by a reported J PtH , J PtC , or J PtP coupling constant. The term 'Pt-shoulders' refers to signals exhibiting coupling to 195 Pt where the satellites are not resolved from the parent signal. The following abbreviations are used: s = singlet, d = doublet, t = triplet, sept = septet, m = multiplet, ov = overlapping AB (subscript) indicates a second order AB spin system, v = virtual. S.1.2 Ligand Syntheses: S4 General Procedure for Preparation of Diorganophosphine Reagents Ad 2 PH was prepared from adamantane and PCl 3 as reported previously. 3 While commercially available, we found that Ph 2 PH, i Pr 2 PH, and t Bu PH were more economically prepared by treatment of an appropriate diorganophosphine chloride (R 2 PCl) with LiAlH 4. Caution: treatment of neat i Pr 2 PCl and Ph 2 PCl with LiAlH 4 is exothermic and must be done slowly to avoid vaporization of the phosphine. Example procedure: A Schlenk flask was charged with i Pr 2 PCl (5.0 g, 0.032 mol) and a stir bar under an atmosphere of N 2 and cooled to 0 °C. Solid LiAlH 4 (0.80 g, 0.021 mol) was added in ~50 mg portions over a period of an hour. The reaction was allowed to warm to room temperature after the addition was complete, and was stirred for 16 hours. Vacuum distillation of the product provided 1.58 g (41%) of i Pr 2 PH. Synthesis of L 1 (Ph 2 PCH 2 NMe 2) A reaction vessel fitted with a Teflon screw-cap and equipped with a stir bar was charged with Ph 2 PH (2.36 g, 0.013 mol) and paraformaldehyde (0.38 g, 0.013 mol 'H 2 CO'). A solution of HNMe 2 (0.013 mol, 2.0 M in MeOH) was added by syringe with stirring. The reaction vessel was heated to 60 °C for 9 h. The product was collected by distillation (bp. 348 °C), providing L 1 as a colourless oil. Yield 2.94 g (89%). The NMR data is similar to that previously reported in the literature.
Nucleophilic substitution in tris(pentafluorophenyl)phosphine
Canadian Journal of Chemistry, 1979
Reaction of tris(pentafluorophenyl)phosphine with various nucleophiles (DMF, HMPA, HEPA, diethylformamide, hydrazine, UDMH, phenylhydrazine, formamide, and aniline) gave exclusively the replacement of all three para fluorines with the exception of aniline, phenylhydrazine, and formamide which gave mixtures of the mono- and bis-4-substituted phosphines. Sodium bisulphide and various alkoxides led mainly to C—P bond rupture though some alkoxides did under certain conditions give some of the expected substitution product. 19F, 31P, and 1H nmr and mass spectral data are presented.
Inorganic Chemistry, 1999
An improved preparation of 4-(dichlorophosphino)-2,5-dimethyl-2H-1,2,3σ 2-diazaphosphole (1) is described. Replacement of the two chlorine substituents with two fluorine (2), dimethylamino (3), diethylamino (4), bis(npropyl)amine (5), pyrazole (9), 3,5-dimethylpyrazole (10), 2,2,2-trifluoroethoxy (11), phenoxy (12), pentafluorophenoxy (13), 2,6-difluorophenoxy (14), and pentafluorobenzoxy (15) substituents has been accomplished to create a large suite of potentially bifunctional phosphorus(III) ligands with two-and three-coordinate P centers spanning a range of basicity and steric bulk at the exo-phosphorus center. Bulky secondary amines (such as diisopropylamine, dibenzylamine, and iminodibenzyl) replaced only one chlorine atom to give asymmetric 4-(chloroaminophosphino)-2,5-dimethyl-2H-1,2,3σ 2-diazaphospholes (6, 7, and 8, respectively). The asymmetric substitution creates a diastereotopic center in both 6 and 7 which is observed as fluxional NMR behavior at room temperature. Similar diastereotopic induced behavior was observed in the substituent methylene protons of 11. Coordination studies of the fluorinated phosphole (L) 2) with Cr(0) and Mo(0) gave Cr(CO) 5 L (16), cis-Mo-(CO) 4 L 2 (17), and fac-Mo(CO) 3 L 3 (18) (where L) 4-(difluorophosphino)-2,5-dimethyl-2H-1,2,3σ 2-diazaphosphole). The fluoro ligand displays a behavior which is similar to that of PF 3 and phosphites.
Journal of Fluorine Chemistry, 1995
5,6-Benzo-1,3-dimethyl-W-2-oxo-1,3,2A4-diazaphosphorinan-4-one (1) and 1,3,5-trimethyl-2H-2-oxo-l,3,5-triaza-2A4-phosphorinan-4,6-dione (2) were allowed to react with perfluoro-isobutylmethyl ketone (4), perfluoro-l-methyl-2-isopropyl diketone (5) and perfluoro-1-methyl-2-n-propyl diketone (6), leading to the products 7-12 by formation of a P-O-C bond and migration of the hydrogen atom from phosphorus to the carbonyl carbon atom as a result of an O-addition reaction. In the reaction of 2 with 6, the formation of two isomers 12a and 12b was observed. Reaction of a mixture of 12a and 12b with water led to 2-hydroxy-2-oxo-triazaphosphorinan-4,6-dione (15) and two further perfluorinated products 13 and 14. Dimethylphosphine oxide (3) reacted with perfluoro-isobutylmethyl ketone (4) to give the perfluoroalkyl-substituted cu-hydroxyphosphine oxide 16. In contrast to 7-12, compound 16 was shown to contain the P-C-OH fragment rather than a P-O-C bond. The existence of 7-9 in diastereomeric pairs and of 16 as an enantiomeric pair has been established by 'H, 13C and "F NMR spectroscopy. All compounds were characterized by NMR spectroscopy, mass spectrometry and elemental analysis. X-Ray crystal structure analyses have been carried out for the substituted diaza-and triaza-phosphorinanones 9 and 11. Compound 9 crystallizes as two independent molecules, which are, however, closely similar. Hydrogen bonds of the form C-H.. . .O are observed for 9 and (weakly) in 11; the fluorine substituents presumably make the chain H atoms more positive.
Inorganica Chimica Acta, 2000
The fluorinated phosphine ligands [PR 2 R f (R=Cy (2); i Pr, (3); Ph, (4); R f = CH 2 CH 2 (CF 2 ) 5 CF 3 ] react with Fe(CO) 3 (BDA) (1) (BDA = (C 6 H 5 )CH=CHC(O)CH 3 , benzylideneacetone) to yield the corresponding Fe(CO) 3 (PR 2 R f ) 2 (R =Cy, (5) i Pr, (6) Ph, ) complexes. Infrared studies on the carbonyl complexes and solution calorimetry studies of the reaction of 1 with 2, 3 and 4 have been performed to quantify the donor strength of this series of ligands.