Phosphine triphenyl-, complexes with

This material may be converted directly to a phosphonium salt 1.40 g. (0.0054 mole) of the crude iodide is dissolved in 20 ml. of benzene, and 1.42 g, (0.0054 mole) of triphenylphosphine [Phosphine, triphenyl-] is added. On standing, 2.5 g. (77%) of the triphenylphosphonium salt precipitates as a colorless 1 1 complex with benzene, m.p. 135-137°. Recrystallization from methanol-benzene raises the melting point to 140-142°. Analysis calculated for C28H29PI CeH6 C, 68.23 H, 5.39. Found C, 68.15 H, 5.28. 

In the presence of air, trimethyl, triethyl, and tributylphosphine combust spontaneously. In the presence of pure oxygen, even though it was at a low temperature, triethylphosphine detonated. In the same conditions, triphenyl-phosphine does not seem to be dangerous. Trimethylphosphine can be stored safely in the air in the form of a complex with silver iodide. 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

C27H23Cl2N03PRe, Rhenium(V), dichloro(2-(2 -hydroxyphenyl)-2-oxazoline)(triphenyl-phosphine) 0x0-, 34 58 C27H50P2, dcpp, l,3-bis(dicyclohexylphosphi-no)propane, complex with copper(I), 34 177... 

Phenylurefbanes, 58, 10 Phosgene, 57, 46 Phosphine, diphenyl-, 56,45 Phosphine-mckcl catalyst, 58, 129 PHOSPHINE-NICKEL CATALYZED COMPLEX CROSS-COUPLING OF GRIG-NARD REAGENTS WITH ARYL AND ALKENYL HALIDES, 58, 127 Phosphine, phenyl-, bis(3-dimethylamino-piopyl)-, 55, 128 Phosphine, triphenyl-, 56, 81 Phosphomum, [ 4-(4-rne thoxy phenyl)-2-butenyl) triphenyl, iodide, 56, 81 Phosphomum, 2-octadecenyltnphenyl-, iodide, 56, 81... 

Sterically bulky chelating diphosphines such as (/ )-Ph2PCHMeCH2PPh2 [(/ )-PROPHOS] form ruthenium complexes with P—Ru—P bond angles considerably smaller than those exhibited for the analogous triphenyl-phosphine complexes, often less than the idealized 90°. This is a consequence of constraints on the bite angle of the two phosphorus atoms... 

Triphenyl phosphine coordinates germanium(II) chloride or iodide " to form 1 1 complexes with tbp geometry at the metal and bond lengths Ge—P 2.511 A and 2.507 A, respectively. These complexes are in some ways analogous to ylides (R 3P = CR ) and have some properties in common with these lighter homologues. 

The results summarized in Table 25 show that nickel complexed with a bidentate phosphine [NiCl2[Ph2P(CH2)3PPh2]j is less efficient than nickel complexed with triphenyl phosphine [NiCl2(PPh3)2] and the selectivity in favor of the 5, 2 product is moderate in both cases, even with primary sulfides. In the sole examples of cinnamyl methyl sulfide, the selectivity is excellent toward the 8, 2 product 276. 

A related group of compounds is that of the gold(III) dimethyl(alkoxycarbonyl) complexes, accessible by the reaction of carbon monoxide with dimethyl(alkoxy)(triphenyl-phosphine)gold(III), which is prepared in situ from cw-[AuIMe2(PPli3)] and sodium alkoxide in methanol (equation 80)353,359. Thermolysis of the methoxycarbonyl complex in benzene leads to the reductive elimination of methyl acetate and ethane, indicating competition between the two modes of decomposition illustrated in Scheme 27. The reaction of the same complex with electrophiles such as hydrogen chloride proceeds with liberation of carbon monoxide and methanol, as illustrated in equation 81. 

Phosphorus oxychloride, which forms stable and often insoluble complexes with Friedel-Crafts catalysts, appears not yet to have been used with success in reactions of this type. The analogous reaction of thiophosphoryl chloride has been studied in detail, but only recently 158 its use has made phenyl(thio-phosphonic) dichloride, diphenyl(thiophosphinic) chloride, and triphenyl-phosphine sulfide conveniently accessible. The dichloride is obtained in about 45% yield, together with about 33% of the monochloride, when a mixture in the molar proportions PSC13 A1C13 C6H6 = 1 2 1 is heated at 80° for 15 min the ratios 1 2 4 are most favorable for preparation of the mono-... 

The pentan-2,4-dionato (acac) complexes may be prepared either by cleaving dinuclear pentan-2,4-dionato complexes with tertiary phosphines, or by displacing the halo ligands in bridged, triphenyl phosphite or PFjCNEtj) complexes (equations 12-16). - ... 

X = Cl. Br. T Treatment of polystyryl diphenylphosphine with CL, Br, or I, in CH,CL.24 Halohydrins from epoxides yields and selectivities compare well with those obtained with monomeric triphenyl phosphine-halogen complexes.2 11 Open and cyclic acetals and thioacetals by treatment of aldehydes and ketones with alcohols or thiols in the presence of polystyryl diphenylphosphine iodine complex.249... 

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