Phosphination dichloromethane

SORPUK Tris(2,4,6-trimethoxyphenyl)(diiodine)phosphine dichloromethane solvate 2.483 3.340 174.50 I... 

To a mixture of 100 ml of dry dichloromethane, 0.10 mol of propargyl alcohol and 0.11 mol of triethylamine was added a solution of 0.05 mol of Ph2PCl in 75 ml of dichloromethane in 3 min between -80 and -90°C. The cooling bath was removed, and when the temperature had reached 10°C, the reaction mixture was poured into a solution of 2.5 ml of 362 HCl in 100 ml of water. After vigorous shaking the lower layer was separated and the aqueous layer was extracted twice with 25-ml portions of dichloromethane. The combined solutions were washed twice with water, dried over magnesium sulfate and then concentrated in a water-pump vacuum, giving almost pure allenyl phosphine oxide as a white solid, m.p. 98-100 5, in almost 1002 yield. 

However an unexpected new cyclic ruthenium phosphorus ylide half-sandwich complex 42 has been obtained by reaction of 41 with dichloromethane as solvent [79]. The cyclisation involves a C-Cl activation and corresponds to the incorporation of the methylene moiety in the P-C bond and to the ortho-metal-lation of one phenyl of the phosphine. An other novel unusual phosphonium ylide ruthenium complex 43 has also recently been described [80]. 

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. 

An extension of the research on silver complexes with Lewis base-functionalized mono(A-heterocyclic carbene) ligands has been made toward the better-studied and stronger coordinating phosphine systems. The reaction of a diphenylphosphine-functionalized imidazolium salt with silver oxide in dichloromethane affords a trinuclear silver carbene complex 50, as confirmed by electrospray-ionization mass spectrometry.96,97 Metathesis reaction of 50 in methanol using silver nitrate gives 51 in 33% yield. The crystal structures of 51 were found to be different when different solvents were used during crystallization (Scheme 12).97 One NO3- anion was found to be chelated to... 

As a further confirmation that cuboidal tetramanganese complexes can be redox active, the phosphinate derivative [Mn404(02PPh2)6] illustrated in Figure 46 displays in dichloromethane solution a quasireversible Mn2inMn2IV-MnUIMn3IV oxidation ( ° = +1.08 V ra. SCE).65... 

Like its monomeric counterpart, the polymeric reagent is inert to simple amines, amides, alcohols and phenols, but easily oxidizes thiols to disulphides, phosphines to phosphine oxides, hydroquinone and catechol to quinones, and thioketones, thioesters and trithiocar-bonates to the corresponding 0x0 derivatives, in dichloromethane, chloroform or acetic... 

From Azides and x-Acylphosphorus ylids Addition of azides to a-acylphosphorus ylids takes place at room temperature in dichloromethane or at 80°C in benzene, giving triazolines from which a phosphine oxide is spontaneously eliminated. " The ylids exist almost exclusively in the cis-enolate configuration, and a mechanism involving concerted 1,3-dipolar addition has been proposed (Scheme 12) on the basis that there is a low entropy of activation for the reaction, and that the reaction rate is insensitive to changes in solvent polarity. ... 

P-Donor Ligands. and n.m.r. studies of tertiary phosphine adducts of TiCl4 in dichloromethane solution suggest the existence of fast, temperature-dependent equilibria involving the 1 1 (trigonal-bipyramidal) and 1 2 cis-octahedral) TiCl4-PR3 adducts and free PR3 (R = Me, Et, Pr, Bu, Ph, or cyclohexyl). Several of these 1 1 and 1 2 adducts have been isolated for the first time and characterized by analysis and i.r. spectroscopy. At low temperatures (cfl. 210 K) there is some evidence for the formation of dimeric species, formulated as [ClaTiCljTiClaPRa]. ... 

The palladium catalyst supported on the dendrimer with 24 phosphine end groups (2) was used in a CFMR. In the continuous process a solution of allyl trifluoroacetate and sodium diethyl 2-methylmalonate in THF (including -decane as an internal standard) was pumped through the reactor. Figure 4 shows the conversion as a function of the amount of substrate solution (expressed in reactor volumes) pumped through the reactor. The reaction started immediately after the addition of the catalyst, and the maximum conversion was reached after two reactor volumes had passed, whereupon a drop in conversion was observed. It was inferred from the retention of the dendrimer (99.7% in dichloromethane) that the decrease was not caused by dendrimer depletion, and it was therefore ascribed to the... 

The second bright yellow band separates from the third yellow band with 15% benzene-hexane. Removing the solvent and recrystallizing the residue from dichloromethane-hexane yields the secondary metallation products 2 (0.08g, O.lOmmol) and 3 (0.12g, 0.14mmol), respectively. These are the phosphine-substituted derivatives of the secondary metallation product described below. The yield of these two products may be maximized by heating the starting complex in the absence of solvent to 145 °C (whereupon it melts) for 15 to 20 min. 

Dichloro(thiocarbonyl)tris(triphenylphosphine)osmium(II) (2.0 g), triphenyl-phosphine (0.1 g) and sodium hydroxide (0.5 g) are combined with 2-methoxy-ethanol (20 mL) in a 100-mL flask, under a nitrogen atmosphere. The mixture is heated to reflux with stirring and maintained at reflux for 20 min. The resulting suspension is cooled on ice. Filtration gives white crystals, which are redissolved in dichloromethane and filtered through a Celite pad. Ethanol is added, and the dichloromethane is removed under reduced pressure. Filtration gives white crystals, which are washed with absolute ethanol (4 x 25 mL) and hexane (4 x 25 mL) and dried at room temperature. Yield 1.22-1.72g (65-91%). 

Stable 1 1 complexes of the type R3PAg(0C103) have been isolated using bulky phosphines such as PBu3, PCy3 (Cy = cyclohexyl) and P(o-MeC6H4)3 as well as with the less bulky triphenylphosphine and para-substituted triarylphosphines.181 On the basis of molecular weight measurements and also their IR spectra, it was concluded that they had linear two-coordinate monomeric structures in which the perchlorate ion was coordinated to the silver in both the solid state and in dichloromethane solution.181... 

---