Diphenyl sulfoxide complexes

Diphenyl sulfoxide complexes of uranium(VI) have been reported (495) and a thorough infrared and conductivity study detailed (433), suggesting that the thiocyanate complexes of empirical formula [U02(R2S0)2(NCS)2] are in fact dimeric with bridging iV S-NCS ligands. 

The current status of knowledge concerning these dimethyl sulfoxide and diphenyl sulfoxide complexes is thus rather uncertain and is typical of many complexes of this class. Most of the complexes have not been subjected to extensive study by physical chemical means. In general, the compounds have been characterized only through measurements of the molar conductivity and infrared spectra. Additional work, particularly measurements of the absorption and emission spectra and ultimately structure determinations by x-ray diffraction, wiU be necessary to resolve these uncertainties. 

Likewise, pyridines such as methyl isonicotinate 1999 or quinolines are readily oxidized by BTSP 1949 in the presence of HOReOs in CH2CI2 to give, after 6 h at 24°C, 98% yield of, e.g., methyl isonicotinate N-oxide 2000 [174] (Scheme 12.49). The oxidation of diphenylsulfide with BTSP 1949 and triphenylphosphine dichloride in acetonitrile results, after 60 h at room temperature, in only 12% diphenyl sulfoxide 2001 and 88% recovered diphenyl sulfide [175] (Scheme 12.49), whereas thianthrene 5-oxide 2002 is oxidized by the peroxy-Mo complex 2003 to give 58% of a mixture of 2004 to 2007 in which the trans 5,10-thioxide 2005 predominates [176] (Scheme 12.50). 

With diphenyl sulfoxide, Ln(DPS0)g(C104)3 complexes containing ionic perchlorate and Ln(DPSO)8l3 for Ln = La-Y have been reported [221,222], The above on repetition yielded Ln(DPS0)7(C104)3 for Ln = Sm, Eu, Yb. This family of complexes lack structural data. 

C12H10Cl2O8Te Telluran(IV) Diperchloryloxy-diphenyl (Dimethyl Sulfoxide Complex) EI2b, 619 (Cl - O-CIO3)... 

Diphenyl Tellurium Diperchlorate/Dimethyl Sulfoxide Complex A mixture of 0.70 g (2 mmol) diphenyl tellurium dichloride, 0.83 g (4 mmol) silver perchlorate and 30 ml dichloromethane is stirred at 20° for 1 h. The precipitated silver chloride is removed by filtration. The filtrate is mixed with a solution of 0.15 g (2 mmol) dimethyl sulfoxide in 10 ml dichloromethane. The mixture is refluxed for 5 h. The solvent is distilled from the mixture. The residue is treated with petroleum ether (40-60°). The resulting white solid is recrystallized from petroleum ether (40-60°)/dichloromethane (3 1) and then dried under reduced pressure 95% yield m.p. 140°. 

The arylsulfonium metal halide complex salts are not readily available. Triphenylsulfoniurn hexafluorophosphate can be prepared from diphenyliodonium hexafluorophosphate by heating with phenyl sulfide, as described by Knapczyk and McEwen ( ), or by reaction of phenyl magnesium bromide with diphenyl sulfoxide followed by reaction with hexafluorophosphoric acid according to the procedure of Wildi, Taylor and Potratz (60). 

OPSijCiiHj, Phosphine, [2,2-dimethyl-l-(trimethylsiloxy)propylidene](tri-methylsilyl)-, 27 250 OP3RhC55H44, Rhodium(I), carbonylhy-dridotris(triphenylphosphine)-, 28 82 0SC,2H (, Diphenyl sulfoxide, nickel complex, 29 116... 

Complexes of diphenyl sulfoxide exhibit S—O stretching frequencies ranging from 931 cm for Fe" to 1012cm for Mg". The IR spectra of the metal complexes of tetrahydrothiophene oxide (32) show that the complexes of Co", Ni" and Cu" are O-bonded, while those of the (b) class metal ions Pd" and Pt" are S-bonded. ... 

Electrophilic Aromatic Substitution. When activated with electrophilic reagents, such as trifluoroacetic anhydride (TFAA), diphenyl sulfoxide is converted into an acyloxysulfonium ion, which can effect electrophilic aromatic substitution. When this mode of sulfoxide activation is performed in the presence of simple aromatic substrates, such as o-xylene, the corresponding triarylsulfonium salt is formed in good yield (eq 4). The Ph2SO TFAA reagent combination reacts similarly with more complex substrates, such as indoles, affording the 3-indolylsulf-onium salts. 

Klaeboe, P. (1964) Spectroscopic studies of charge transfer complexes. X. Methyl phenyl sulfoxide and diphenyl sulfoxide with iodine. Acfa Chem. Scand., 18, 999-1005. 

A further illustration of the difficulties inherent in the synthesis of these types of complexes is illustrated by diphenyl sulfoxide. The perchlorates were reported to combine with only six ligands to give R(DPS0)6(C104)3 which existed for all the lanthanides with only ionic perchlorate ions (Ramalingam and Soun-... 

Serra, O.A. and L.C. Thompson, 1973, Rare Earth Complexes of Diphenyl Sulfoxide, in C.J. Kavane and T. Moeller, eds.. Proceedings of the Tenth Rare Earth Research conference (National Technical Information Service, Washington, D.C.) pp. 325-333. Serra, O.A. and L.C. Thompson, 1976, Inorg. Chem. 15, 504-507. 

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