Solubility of phosphines

The solubility of phosphine in water is, in comparison to ammonia, very small At 17 °C, only 22.8 ml of gaseous phosphine dissolve in 100 ml of water. ... 

According to earlier results, the solubilities at 18 °C in ethanol, ether and oil of turpentine are 0.5, 2 and 3.25 volumes of phosphine per volume of solvent, respectively Phosphine dissolves in cyclohexanol far more readily than in water. At 26 °C and a partial pressure of 766 mmHg, 2856 ml of phosphine dissolve in 1000 ml of cyclohexanol 15,900 ml of phosphine dissolve in 1 litre of trifluoroacetic acid at 26 °C and a pressure of 653 mmHg3 1. For the solubilities of phosphine in non-polar solvents see 312. jis)... 

Based on the inversely temperature-dependent solubility of phosphines modified with polyoxyethylene chains, TRPTC has been proposed, and applied to the aqueous/organic two-phase reaction system [11], The general principle of TRPTC is depicted in Figure 1. 

Olivier-Bourbigou s group, for example, has recently shown that phosphite ligands can be used in Rh-catalyzed hydroformylation in ionic liquids as well as the well loiown phosphine systems [81]. Since phosphite ligands are usually unstable in aqueous media, this adds (apart from the much better solubility of higher olefins in... 

Extractants derived from the carbamoylmethylphosphoryl moiety (CMP) were studied in the phosphonate, phosphinate, and phosphine oxide classes. Our studies focused on dihexyl-N,N-diethylcarba-moylmethylphosphonate, DHDECMP, hexyl hexyl-N,N-diethylcarbamoyl-methylphosphinate, HHDECMP, and octyl(phenyl)-N,N-diisobutylcarba-moylmethylphosphine oxide, 0D[ IB]CMP0. The three types of CMP extractants were compared on the basis of nitric acid and extractant dependencies for Am(III), solubility of complexes on loading with Nd(III) and U(VI), and selectivity over fission products. On the basis of the above data two conceptual flowsheets were developed. The first flowsheet involves the extraction of all of the actinides from HLLW using 0.4 M 0D[IB]CMP0 in DEB. The second flowsheet involves the extraction of all of the actinides from dissolved spent LWR fuel using 0.8 M DHDECMP in DEB. 

This review account will summarize latest research results on the design, development and properties of functionalized primary phosphines. In particular, the focus would be centered around recent results from our laboratory on the chemical architecture of heteroatom functionahzed primary bisphosphines. We wiU also discuss synthetic protocols for the formylation reactions of functionalized primary phosphines to produce structurally diverse water-soluble hydroxymethyl phosphines. Finally, we will discuss the utility of carboxylate functionahzed primary bisphosphines for incorporation on to peptides and their potential apphcations in catalysis and biomedicine. 

Several t-alkylphosphines have been oxidized by aqueous alkali, resulting in the evolution of hydrogen gas. The only requirement for reduction appears to be the solubility of the phosphine in aqueous alkali... 

The anaerobic oxidation of phosphines to their oxides by hydroxide ion has been shown to involve the liberation of hydrogen, possibly from the intermediate (21). These oxidations were studied with water-soluble phosphines, since solubility was found to be the main factor controlling the rate of oxidation. The preparation, and detailed n.m.r. spectrum, of PP-dimethyl-P P -diphenyldiphosphine disulphide (22) is a relatively rare example of a study of a mixed disulphide. Many examples of routine oxidation of phosphines to their oxides have appeared. These include the preparation of polyhalogenoarylphosphine oxides using dichromate... 

Nickel(II) salts are able to catalyze the coupling of Grignard reagents with alkenyl and aryl halides. A soluble 6 -phosphine complex, Ni(dppe)2Cl2, is a particularly effective catalyst.266 The main distinction between this reaction and Pd-catalyzed cross... 

Miscellaneous Reactions of Phosphines.- The role of chiral phosphines as ligands in the catalysis of reactions leading to the formation of chiral products has been reviewed.1111 A procedure for the determination of the enantiomeric excess in chiral phosphines has been developed, based on 13C n.m.r. studies of the diastereoisomeric complexes formed by phosphines with the chiral pinenyl nickel bromide complex. 111 Studies of the sulphonation of triphenylphosphine and of chiral arylphosphines have been reported in attempts to prepare water soluble ligands which aid... 

Hydroaminomethylation of alkenes occurred to give both n- and /. so aliphatic amines catalyzed by [Rh(cod)Cl]2 and [Ir(cod)Cl]2 with TPPTS in aqueous NH3 with CO/H2 in an autoclave. The ratio of n-and /.soprimary amines ranged from 96 4 to 84 16.178 The catalytic hydroaminomethylation of long-chain alkenes with dimethylamine can be catalyzed by a water-soluble rhodium-phosphine complex, RhCl(CO) (Tppts)2 [TPPTS P(m-C6H4S03Na)3], in an aqueous-organic two-phase system in the presence of the cationic surfactant cetyltrimethy-lammonium bromide (CTAB) (Eq. 3.43). The addition of the cationic surfactant CTAB accelerated the reaction due to the micelle effect.179... 

More recently, Atwood et al. developed a platinum complex of a water-soluble, bidentate phosphine ligand, cA-(TPPTS)2PtCl2 [TPPTS = tris(sodium m -benzenesuI onatc)phosphi nc, as an effective hydration... 

The effectiveness of platinum(O) complexes of phosphines as catalysts has led to the synthesis of a wide variety of complexes with phosphines that confer solubility in a range of solvents or have... 

The red and orange forms of RhCl[P(C6H5)3]3 have apparently identical chemical properties the difference is presumably due to different crystalline forms, and possibly bonding in the solid. The complex is soluble in chloroform and methylene chloride (dichloromethane) to about 20 g./l. at 25°. The solubility in benzene or toluene is about 2 g./l. at 25° but is very much lower in acetic acid, acetone, and other ketones, methanol, and lower aliphatic alcohols. In paraffins and cyclohexane, the complex is virtually insoluble. Donor solvents such as pyridine, dimethyl sulfoxide, or acetonitrile dissolve the complex with reaction, initially to give complexes of the type RhCl[P(C6H6)3]2L, but further reaction with displacement of phosphine may occur. 

Considerable work has been conducted on a water-soluble catalyst using sulfonated phosphine-modified rhodium. Details of this chemistry will be described in Chapter 5. The general concept (Figure 2.3) is to make the catalyst water soluble, then after product formation, decant the product. In order for the water-soluble catalyst to be effective, the alkene must dissolve in the aqueous layer. This has been demonstrated on a commercial basis using propene. The low solubility of higher alkenes in the aqueous catalyst layer has proven problematic. The desirable characteristic of the ligand, water solubility, is needed in the separation step but is a disadvantage in the reaction step. 

The concept makes use of the complimentary strengths and weaknesses of the two unconventional media. While ionic liquids are known to be excellent solvents for many transition metal catalysts, the solubility of most transition metal complexes in scC02 is poor (if not modified with e. g. phosphine ligands with fluorous "ponytails" [64]). However, product isolation from scC02 is always very simple, while from an ionic catalyst solution it may become more and more complicated depending on the solubility of the product in the ionic liquid and on the product s boiling point. 

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