Phosphine, chloro

Miscellaneous spectral studies include e.s.r. spectra of chloro-phosphines (2)6 and vibrational spectra of various phosphines.6-8 N.m.r. studies include those of borane complexes of aryldichlorophosphines,9 and studies of the conformation of dichloro-(isopropyl)phosphine (3)10 and dichloro(ethyl)phosphine (4).10 These phosphines have the preferred conformations shown. Conformation has also been the theme of electron-diffraction work on the anhydride (5), which appears to have a staggered conformation.11 The electronic implications of a relatively short P—O bond and wide POP angle have been discussed.11... 

When diphosphines are heated with carbon tetrachloride at 120—140 °C, chloro-phosphines are formed, together with trichloromethyldialkylphosphines (ll).17... 

Tetraiododiphosphine (9) has been used to remove hydroxy-groups from 1,4-diols, as shown in the preparations of (55)15 and (56).4e Yields of 75 % have been obtained in the conversion of chloro-phosphines into phosphinates (57), by treatment with an alcohol-base mixture in carbon tetrachloride.47... 

Mach isolated a crystalline stericaUy uniform substance, m.p. 77-78,5 °C, identified as 4-chloro-phosphinic acid chloride 94. 1.1.1.4-Tetra-chloro-2.4.6-tri-tert-butyl-X -phosphorin 93 is assumed to be the primary chlorination product. 

In the course of a study of the formation of fluorophosphoranes from chloro-phosphines (22) we observed one exception in the compound chloromethyldi-chlorophosphine, which reacted smoothly with antimony trifluoride to give the flammable fluorophosphine, C1CH2PF2, under conditions where many other chloro-phosphines were invariably converted into fluorophosphoranes. As this fluorophosphine is readily available, its interaction with a metal carbonyl derivative was studied, and cycloheptatriene molybdenum tricarbonyl, obtained from the reaction of molybdenum hexacarbonyl with cycloheptatriene (I, 2), was chosen as a starting compound. 

Fluorophosphinenickel(O) complexes can be formed by reaction of the corresponding chloro-phosphine complexes with potassium fluorosulfinate (equations 9 and 10).1718 The metal inhibits oxidation of the ligand to the phosphinic fluoride, a reaction that occurs readily to the free ligand. 

Both chloro phosphines, tert-C4 H9 PC12 and (fert-C4H9 )2PC1, are very sensitive to air and moisture and must be handled in a... 

Phosphines and phosphides react rapidly with positive halogen and hence polyhalogen compounds, e.g. tetrachloromethane, are particularly suitable and have the advantage that the chloro-phosphine formed is rapidly attacked by the nucleophile. In principle therefore the phosphorus atoms can be fully substituted by reactions of the following type,... 

Continued research on N-silyl-phospha-amidines and N,N-bis-silylated phosphaguanidines (5) led us to carbosilylated phos-phaalkenes. The various routes to trimethylsilylmethyl-chloro-phosphines and their conversion into carbosilylated phospha-alkenes is given in Scheme 4 (6). Interaction of these products with hydrogen chloride leads to Si2CH-PRCl and Si-CH2-PRC1, respectively. By HC1 abstraction from these products, the parent... 

Preparations and reactions of some mono(trialkylsilyl)phosphines, which derived from bis(trialkylsilyl)phosphines, were described in Sections II.A and II.B. Other preparative methods of mono(trialkylsilyl)phosphines are described in Reference 10. Reactions of some mono(trialkylsilyl)phosphines with hexachloroethane or phosgene lead to chloro-phosphines (equation 42)66. It should be noted that treatment of bis(trialky lsilyl)phosphines... 

The synthesis of the fluoro phosphines is accomplished using chlorine-fluorine exchange in the corresponding chloro phosphines with sodium fluoride in sulfolane (tetrahydrothiophene 1,1-dioxide). The preparation of representative fluoro phosphine complexes with both a zero-valent and bivalent transition metal, Mo(0) and Ni(II), respectively, is also described. 

The reaction is conducted in a 250-mL, three-necked flask, fitted with a mechanical stirrer, a thermometer reaching close to the bottom of the flask, and a 25-cm Vigreux column to which has been connected a distillation head with multiple receiver. tert-Butyldichlorophosphine (31.8 g, 0.2 mole) is added to a stirred suspension of NaF (25.2 g, 0.6 mole) in 100 mL of sulfolane over a period of 1 hour. A slow stream of nitrogen is passed through a T-tube connected to the outlet of the distillation apparatus. After the addition of the chloro-phosphine, the reaction mixture is heated as follows 45 minutes at 80°, 15 minutes at 100-180°, and 30 minutes at 180°. Distillation of the fluorophosphine commences at 80° and is complete at 180°. The product is collected in a receiver flask cooled in Dry Ice. fer -Butyldifluorophosphine is obtained as a colorless liquid of bp 41-44° the yield is 20-23 g (79-91%, based on tert-butyl-dichlorophosphine ). Anal. Calcd. for C4H9F2P P, 24.6 F, 30.2. Found P, 24.1 F, 29.0,... 

The reaction of trichlorogermylphosphines (226) with DBU gave chloro-phosphine 227 and a DBU -germanium dichloride complex (228) (84CC1621). 

The cleavage of the Si—N bond in iV-silylphosphazenes generally provides a versatile means of changing the iV-substituents. However, reactions with chloro-phosphines are more complex in that a rapid quatemization step may occur, e.g. 

Some ditcchnctium(II) chloro phosphine complexes were synthesized by reduction of the corresponding TeCU phosphine compounds in benzene or THF with finely divided metallic Zn ... 

Preparation. - Fluorophosphines have been obtained from the reactions of the related chlorophosphines with trimethyl tin fluoride. Phenyl(isopropyl)-fluorophosphine has been resolved via a chiral amine-palladium(II) complex, providing the first example of the resolution of a free fluorophosphine chiral at phosphorus. This compound racemises at 20 °C in benzene solution over six hours. The neat compound rapidly decomposes by redox disproportionation. The same approach has been used for the resolution of the related chloro-phosphine, but the optically active compound could not be liberated unchanged from the crystallised diastereoisomeric palladium complex. The dihalo-genophosphines... 

The d trihydrides CP2MH3 (M = Nb, Ta) also give fast reactions with chloro-phosphines leading to symmetrical ionic compounds. The central position of the PR2H group has been unambiguously established by H NMR spectroscopy. ... 

Hindered rotation about the P—C bond is indicated in a recent electron-diffraction study of phenyldichlorophosphine. The reaction of the chloro-phosphines RPClg and RgPCl with trifluoroacetic acid gives the unstable acetoxy-derivatives R,P(OCOCFg)3 , = 1 or 2, R = Et or Ph. On heating, the monoethyl compound loses trifluoroacetic anhydride and carbon monoxide, i.e. 

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