Phosphines triphenylphosphine sulfides

The use of other phosphorus-sulfur reagents for heterocyclic synthesis appears rare. It would be interesting to investigate in more detail the reaction of compounds, such as the phosphine sulfides, with organic substrates. Triphenylphosphine sulfide is an effective sulfur transfer agent, as it converts oxiranes into thiiranes in good yield. The reaction proceeds with retention of configuration.128... 

Tributylphosphine sulfide has been used as a co-catalyst with dicobalt octacarbonyl for the Pawson-Khand reaction. Thermolysis of a mixture of cadmium chloride and trioctylphosphine sulfide at 250 °C has been used as a route to the formation of nanocrystalline cadmium sulfide." A complex of triphenylphosphine sulfide with a silver-tungsten-iodine acceptor has been characterised by X-ray studies. Ferrocenylphosphine chalcogenides have attracted considerable interest as ligands. Complexes of the monophosphino-phosphine sulfide (269) with rhodium have been characterised." The disulfide (270) forms complexes with both gold(i) and gold(iii) acceptors," and a silver(i) complex of the diselenide (271) has been prepared. ... 

Structural and Physical Aspects. - The stability of the various conformers of the phosphines oxides (269)- 211) has received theoretical consideration. A new triclinic polymorph of triphenylphosphine sulfide has been structurally characterised, together with a related triclinic polymorph of triphenylphos-phine. Two reports of the solid state crystal structure of the phenolic phosphine oxide (272) have appeared. A crystallographic study has confirmed that the product of electrochemical oxidation of o-diphenylphosphinoben-zenethiol is the disulfide-bridged bis(phosphine oxide) (273). Solid-state structural studies of the dioxides (274), the (i )-(-I-)-isomer of (275), 1-hexynyl(diphenyl)phosphine oxide,tribenzylphosphine oxide, and tris(t-butyl)phosphine selenide," have also been reported. 

An interesting oxidative addition reaction leading to a pincer-type complex was reported by Matsumura and Inoue et al. [40]. The protocol involves the reaction of a 71-sulfurane (lO-S-3-tetraazapentalene) with Pd(PPh3)4. The hypervalent sulfur is reduced, and at the same time one of the phosphines and Pd(0) are oxidized to triphenylphosphine sulfide and Pd(II), respectively (see Scheme 6). 

Anthrone heated 48 hrs. at 80° with 0,0-diethyl dithiophosphoric acid in benzene 9-anthracenethiol. Y ca. 100%. - Similarly during 100 hrs. Triphenylphos-phine oxide triphenylphosphine sulfide. Y ca. 100%. F. e. s. S. Oae, A. Naka-nishi, and N. Tsujimoto, Chem. Ind. 1972, 575 phosphine sulfides from phosphine oxides with B2S3, retention of configuration at P, s. B. E. Maryanoff, R. Tang, and K. Mislow, Chem. Commun. 1973, 273. 

Diphenyldisulfide reacted slowly while di-(i T,A/ -dimethylaminophenyl) disulfide reacted more readily. When R is ethyl, benzyl, o-nitrophenyl, p-nitrophenyl, dibenzhydryl, benzthiozoyl, 9-fluorenyl, or antipyryl, the disulfide is stable to treatment with triphenylphosphine for 10 hours at 80° C, and no monosulfide is produced. Electron-donoring groups in the phosphine also increase the rate of reaction. Disulfides of the type R(S=)C—S—S—C(==S)—R react very quickly with phosphines. Triphenylphosphine will remove the sulfur from an ethylene sulfide... 

Four-membered rings. The study of the reaction between thiobenzophenone and methylenetriphenylphosphorane177 pointed out the presence of a reactive intermediate, thiaphosphetane, which decomposed either to a thiirane and triphenylphosphine or to the Witting alkene and a phosphine sulfide, depending on the temperature. 

The carbon diselenide and carbon sulfide selenide complexes of platinum(0) can be synthesized from Pt(PPh3)3. Reaction of the compounds with chelating phosphines results in substitution of the triphenylphosphines (equation 541).1866 With COS the C,S-bonded compound Pt(COS)(PPh3)2 is formed from Pt(PPh3)3. The reaction can also be used to prepare the dithiocarbonato complex Pt(S2CO)(PPh3)2.1867... 

Phosphonium salts, formed in the presence of phosphines, are more stable than sulfonium salts. With triphenylphosphine no polymerization of IBVE by triflic acid was observed [250]. Polymerization proceeds slowly only with the most weakly nucleophilic phosphines such as tris(p-chlorophenyl)phosphine. The equilibrium constant is much higher than for sulfides, Kt /p = 10 ° mol/L [141]. In that case, Eq. (29) should be modified to Eq. (33), because only a small excess of phosphine can be used ... 

Tri-n-butyldifluorophosphorane was first obtained upon interaction between tri-re-butylphosphine and hexafluoro-thioacetone dimer.The method described here involves the reaction of tri-n-butylphosphine sulfide with antimony-(III) fluoride. The method is more generally apphcable in the synthesis of difluorophosphoranes from tertiary phosphine sulfides. The only previously reported difluoro-phosphorane, triphenyldifluorophosphorane, was obtained by the reaction of triphenylphosphine or triphenylphos-phine oxide with sulfur(IV) fluoride under autogenous pressure. ... 

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