Phosphine and related compounds

PH3 is an extremely poisonous, highly reactive, colourless gas which has a faint garlic odour at concentrations above about 2 ppm by volume. It is intermediate in thermal stability between NH3 (p. 421) and ASH3 (p. 557). Several convenient routes are available for its preparation  

Hydrolysis of a metal phosphide such as AlP or Ca3P2, the method is useful even 

Pyrolysis of phosphorous aeid at 205-210° under these eonditions the yield of PH3 is 97% though at higher temperatures the reae-tion ean be more eomplex (p. 512) 

Alkaline hydrolysis of PH4I (for very pure phosphine)  

Phosphine has a pyramidal strueture, as expeeted, with P-H 142pm and the H-P-H angle 93.6° (see p. 557). Other physieal properties are mp —133.5°, bp —87.7°, dipole moment 0.58 D, heat of formation A//f —9.6kJ mol (uneertain) and mean P-H bond energy 320kJmol. The free energy ehange (at 25°C) for the reaetion P4(o -white) + = 

The most stable hydride of P is phosphine (phos-phane), PH3. It is the first of a homologous open-chain series P H +2 (n = I-9) the members of which rapidly diminish in thermal stability, though P2H4 and P3H5 have been isolated pure. There are ten other (unstable) homologous series P H (n=3-l0), P H 2 (n = 

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Tri-t-butylphenyl)(trimethylsilyl)phosphine (10a) and its t-butyldimethylsilyl analog (10b) were prepared from (2,4,6-tri-t-butylphenyl)phosphine33 (equation 76)3. Treatment of the silylphosphines 10a or 10b with n-butyllithium led to the formation of silylphosphides 11a and lib3, which were utilized for the reactions shown in Section V. (2,4,6-Tri-r-butylphenyl)(triphenylsilyl)phosphine and related compounds were also prepared starting from Mes PH i (equation 77) and their structures were analyzed27,89. 

P. L. Timms, Chemistry of Transition-metal Vapours. Part I. Reactions with Trifluoro-phosphine and Related Compounds, J. Chem. Soc. A, 1970, 2526-2528. 

Addition of Ammonia and Amines, Phosphines, and Related Compounds... 

The Reactivity of rraR5-[IrCl(CO)L2] (L = tertiary phosphine) and Related Compounds, B. L. Shaw, ibid., p. 251. 

Baillie C, Xiao J (2003) Catalytic synthesis of phosphines and related compounds. Curr Org Chem 7 477-514... 

The acyl phosphonates, acyl phosphine oxides and related compounds (e.g. 81. 82) absorb strongly in the near UV (350-400 nm) and generally decompose by rescission in a manner analogous to the benzoin derivatives.381"285 Quantum yields vary from 0.3 to 1.0 depending on structure. The phosphinyl radicals are highly reactive towards unsaturated substrates and appear to have a high specificity for addition v.v abstraction (see 3.4.3.2). 

The reactions of phosphorus pentachloride and diphenyltrichloro-phosphorane with amines and related compounds are reported in Chapter 9. The n.m.r. spectra of phosphine-phosphorus pentafluoride adducts have been described (see Chapter 11 for details). 

This year s literature has been characterized by an increasing number of papers devoted to theoretical studies of the bonding in phosphine oxides and related compounds, and these are discussed in Section 1. The chemical aspects of phosphine oxides have not shown any major new developments over the past year, and, once again, these have been sub-divided into sections on the preparation and on the reactions of phosphine oxides. 

Phosphine oxide-based olefin synthesis is being increasingly used and is the method of choice in a number of recent syntheses of natural products and related compounds. 

CHAPTER 3 Phosphine Oxides and Related Compounds By B.J. Walker... 

While the Michael-addition of a,P-unsaturated carbonyl and related compounds constitutes one of the most important fundamental synthetic reactions in organic chemistry, the y-addition developed by Trost and Li of nucleophiles to 2-alkynoates catalyzed by a phosphine provides... 

Arene(tricarbonyl)chromium complexes, 19 Nickel boride, 197 to trans-alkenes Chromium(II) sulfate, 84 of anhydrides to lactones Tetrachlorotris[bis(l,4-diphenyl-phosphine)butane]diruthenium, 288 of aromatic rings Palladium catalysts, 230 Raney nickel, 265 Sodium borohydride-1,3-Dicyano-benzene, 279 of aryl halides to arenes Palladium on carbon, 230 of benzyl ethers to alcohols Palladium catalysts, 230 of carboxylic acids to aldehydes Vilsmeier reagent, 341 of epoxides to alcohols Samarium(II) iodide, 270 Sodium hydride-Sodium /-amyloxide-Nickel(II) chloride, 281 Sodium hydride-Sodium /-amyloxide-Zinc chloride, 281 of esters to alcohols Sodium borohydride, 278 of imines and related compounds Arene(tricarbonyl)chromium complexes, 19... 

Chiariza, R., Horwitz, E.P. 1986. Hydrolytic and radiolytic degradation of octyl(phenyl) butyl carbamoylmethyl phosphine oxide and related compounds. Solvent Extr. Ion Exch. 4(4) 677-723. 

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