Sulfoxide complexes deoxygenation

In addition to the catalysis of sulfoxide deoxygenation (Section IV,C) and sulfoxide oxygenation (Section IV,D), other interesting reactions have been shown to be catalyzed by sulfoxide complexes, and these are detailed below. 

The ability of vanadium(II) chloride to facilitate sulfoxide deoxygenation has been discussed (Section IV,C), and it appears that vana-dium(III) sulfoxide complexes may be prepared by air oxidation of van-adium(II) salts in the presence of the sulfoxide. In this manner, [V(Me2S0)6][C104]3 was prepared from vanadium(II) perchlorate (119) and the kinetics of substitution with thiocyanate ion detailed. Care is necessary in handling the pure compound, as it is reported to be sensitive to detonation. A large number of oxovanadium(IV) species have... 

Among other template transformations, related to modification of ligand systems, it is necessary to indicate reactions of deoxygenation of sulfoxide complexes, for instance (3.195) [417] ... 

Sulfoxides are deoxygenated by BI3 NEt2Ph [23], Sulfides are also cleaved by BI3. Methionine reacts to yield a complex mixture of C-S bond-cleavage products, including homocysteic acid, homoserine, and homoserine lactone [24],... 

The successful deoxygenation of the sulfoxide 18a by either hexachlorodisilane as the reducing agent, or diiron nonacarbonyl according to the deoxygenation-complexation route can also be rationalized in terms of electrophilic attack of the reagents used on the nucleophilic sulfoxy oxygen. 

Complex compounds of sulfoxides Deoxygenation reactions of sulfoxides... 

Problems of dilution and pH sensitivity have also been encountered in the synthesis of cts-[Pt(S-R2SO)(olefin)Cl2] complexes (85), where deoxygenation of the sulfoxide with concomitant oxidation of the metal center occurs at low pH. The reactions of [M(Ph2PCH2CH2PPh2)Cl2] (M = Pd, Pt) with one equivalent of silver perchlorate in the presence of Me2SO yield either the O-Me O complex or its deoxygenation product, depending upon reaction conditions. A sequence of reactions, Eq. (27), has been proposed (143). 

In general, the chemistry of fluoro-l,3,5-triazines resembles that of the chloro derivatives, and therefore will not be discussed in detail. There is evidence that cyanuric fluoride is less reactive than cyanuric chloride in reaction with aniline (76CCC3378). Chambers et al. have reported the isolation of a stable anion cr- complex from the reaction of cyanuric fluoride and cesium fluoride (equation 32) (77JCS(Pl)l605). Such species are believed to be intermediates in the formation of (68) from cyanuric fluoride and perfluoropropene (equation 33). Olah et al. have shown that cyanuric fluoride deoxygenates sulfoxides efficiently (equation 34) (80S221). 

Deoxygenation of sulfoxides. Sulfoxides are converted into sulfides in high yield when treated with 1 eq. of iodine and excess pyridine—sulfur dioxide complex in acetonitrile (80 ). If bromine is used, pyridine is omitted in order to... 

Narayana, C., Padmanabhan, S., Kabalka, G. W. 1991. Reductive dimerization of sulfonyl derivatives to disulfides and deoxygenation of sulfoxides to sulfides using the boron triiodide-A,A-diethylaniline complex. Synlett 125-126. 

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