Phosphorus trichloride metal complexes

Phosphorus tribromide stereochemistry, 36 Phosphorus trichloride metal complexes solvolysis, 418 stereochemistry, 36 Phosphorus trifluoride stereochemistry, 36 Phosphorus trihalides stereochemistry, 36 Phosphorus triiodidc stereochemistry, 36 Photoaquation solid state, 471 Photocalorimetry, 410 Photochemical reactions, 397 applications, 408 mechanisms, 385 solid state, 470 Photochromism, 409 Photolysis... 

At the time of our investigation the only known coordination compounds of chlorophosphines (aside from phosphorus trichloride complexes) were the nickel-(0) compounds, tetrakis(methyldichlorophosphine)nickel-(0) (20) and tetrakis-phenyldichlorophosphine) nickel- (0) (17). Tetrakis (methyldichlorophosphine) -nickel-(0) is noteworthy in that it represents a still rare example of the direct reaction of a ligand with an elemental transition metal to give a complex, while tetrakis (phenyldichlorophosphine) nickel- (0), like tetrakis (trichlorophosphine) -nickel-(0), was obtained readily via the carbonyl. AD chlorophosphine-nickel-(O) complexes, including the phosphorus trichloride complex, Ni(PCl3)4, are compounds relatively stable in the atmosphere, but show poor stability in almost any organic solvent, even under strictly anaerobic conditions. 

Platinum(II)15 and palladium(II)16 complexes of phosphorus trichloride undergo solvolysis in water and alcohols to form complexes with orthophosphorous acid or orthophosphite ligands (equation 6). Similar reactions occur between the palladium(II) phenyldichlorophosphine complex (8) and the diols ethyleneglycol and catechol, but new chelate rings are not formed (Scheme 2). Solvolysis also occurs with attack of diphenylphosphinic acid or a similar diphenylchlorophosphine complex (9) (equation 7). The palladium complexes (8) and (9) are unstable to excess methanol, water or base and undergo reduction. Similarly, the phosphorus trichloride gold(I) complex (10) is reduced by water, but forms stable products on reaction with alcohols (equation 8).15 During the above reactions, the phosphorus—metal bond remains intact and the overall process is one of substitution at phosphorus. 

The chloride2 is a yellowish-white substance, soluble in aqueous alkali-metal chlorides 3 with formation of complex anions, the solutions soon decomposing with precipitation of metallic gold and the formation of complex auric derivatives. The transformation is more rapid in bromide solutions. At 110° to 120° C. aurous chloride and excess of phosphorus trichloride combine to form a double compound of the formula AuCl,PCl3, colourless prisms insoluble in water.4... 

Titanacyclopropenes 31 reacts smoothly with dichlorophosphines or phosphorus trichloride with extrusion of the titanium fragment and formation of the phosphirenes 32 or 33, respectively. The transition metal complexes themselves are generated in situ from either a dichlorotitanium complex (Equation 26) or tetraisopropoxytitanium (Equation 27) by reactions with alkynes <19980M2677>. Analogous chemistry can be carried out with zircona-cyclopropenes <1998CC1177>. 

A general inspection of the Tables of published phosphorus chemical-shift data on co-ordination complexes (in Section VII) indicates the difficulties in any quantitative understanding. In general it appears that the majority of transition metal— phosphine complexes (particularly those containing the metal in its zerovalent state) have resonances at lower field than the corresponding unco-ordinated phosphine. On the other hand the chemical shifts of all phosphorus trichloride complexes occur at higher field than the free ligand, while the behaviour of phosphite complexes is rather more variable. Phosphine... 

The early development of aromatic phosphine chemistry took place during the last quarter of the nineteenth century mainly in Michaelis s school.He prepared dichloro(phenyl)phosphine by the passage of the mixed vapours of benzene and phosphorus trichloride through a red hot porcelain tube. This was quickly followed by the preparation of phenylphosphine, dialkylphenylphosphines, and triphenylphosphine. This latter phosphine was destined some 75 years later to become one of the most important phosphines in the development of homogeneous catalysis by phosphine metal complexes. Michaelis obtained it by the reaction of sodium with dichloro(phenyl)phosphine or phosphorus trichloride and bromobenzene in boiling ether.The development of aromatic phosphorus chemistry rapidly overtook that of their intractable aliphatic analogs. It was well established by the 1920s whereas the aliphatic had to await the... 

Although in this chapter we shall be restricting coverage to reactions of transition-metal complexes, the phenomenon of oxidative addition is not confined to this type of compound. Such reactions are also well established for non-transition metals—a recently reported example concerns the oxidative addition of methyl bromide to indium(i) bromide to give InBr2Me— and for non-metals, as in the reaction of phosphorus trichloride with chlorine, to cite a very familiar example. Likewise, reductive eliminations are known and studied outside the area of transition-metal complexes. One example has been mentioned in Chapter 1 of Part II of this volume, namely the elimination of alkyl halides from the thallium(iii) compounds TlRXa. ... 

Imidophosphoranes (7le) (80JIC1243) or phosphorimidic trichlorides (71f) (79JHC1097) are formed when 2-aminooxadiazoles react with dibromotriphenylphosphorane or phosphorus pentachloride respectively. 2-Amino-l,3,4-oxadiazoles form silver and copper salts and yield complexes with heavy metal salts (62ZC69). 

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