Sulfur—phosphorus bonds

Addition of a phosphorus-sulfur bond to a carbon-carbon triple bond is catalyzed by a palladium(O) complex (Equation (130)).298 Terminal aliphatic alkynes having various functional groups undergo the addition with PhS-P(0)(OPh)2 to afford (Z)-adducts in high yield. In contrast to aliphatic alkynes, phenylacetylene gives a mixture of E Z adducts. Internal alkynes and alkenes are unreactive. 

Phosphorus sulfochloride, 79 42 Phosphorus sulfohalides, physical properties of, 79 43t Phosphorus-sulfur bonds, 79 26-27 Phosphorus tetroxide, 79 52 Phosphorus tribromide, physical properties of, 4 325... 

Degradation of parathion in soil was by hydrolysis to p-nitro-phenol and diethylthiophosphoric acid and reduction to aminopara-thion (25,26). Chemical oxidation of parathion in soils and waters was not prevalent, although oxidation of the phosphorus-sulfur bond has been shown to occur under ultraviolet light and in oxidizing environments (26). At ordinary levels of application to soil, parathion was degraded within weeks if microbial activity was available (27). Accumulations even after repeated applications were unlikely (28). When higher concentrations were applied to soil, persistence increased. Simulated spills of concentrated parathion resulted in a 15% residue after five years (29) and 0.1% after 16 years (30). 

Similarly, the phosphorus-sulfur bond can be generated starting from dialkyl or diaryl phosphites (Eq. (56) Table 4, No. 35)... 

Element-element bonds, addition to G-G multiple bonds arsenic—selenium bonds, 10, 782 boron—boron bonds, 10, 727 boron—sulfur bonds, 10, 778 B-S and B-Ge bonds, 10, 758 chalcogen—chalcogen additions, 10, 752 germanium—germanium bonds, 10, 747 germanium-tin bonds, 10, 780 overview, 10, 725-787 phosphorus—phosphorus bonds, 10, 751 phosphorus—selenium bonds, 10, 782 phosphorus-sulfur bonds, 10, 781 Se-Si and Se-Ge bonds, 10, 779 silicon-germanium bonds, 10, 770 silicon-phosphorus bonds, 10, 780 silicon-silicon bonds, 10, 734 silicon-sulfur bonds, 10, 779 silicon-tin bonds, 10, 770 tin-boron bonds, 10, 767 tin-tin bonds, 10, 748... 

Phosphorus—selenium bonds, alkyne additions, 10, 782 Phosphorus—sulfur bonds, alkyne additions, 10, 781 Phosphorus ylides with gold(I), 2, 275 with trinuclear Os clusters, 6, 740 Phosphoylides, actinide complexes, 4, 203 Photoacoustic calorimetry, in thermochemistry, 1, 612-613 Photoactive molecular devices, and -[RefCO) ,] fragment, 5, 886... 

Halogenolysis of the Phosphorus-Sulfur Bond in Thioloesters of Organic Phosphorus Thioacids... 

The first aliphatic phosphenium cations involving a phosphorus-sulfur bond, e.g. (330) have been prepared and characterised. The stereochemistry, regioselectivity and mechanism of the insertion of the diisopropylamino (chloro) phosphenium cation into the phenylcyclopropane ring, to form phosphetanes, has been studied,Ligand-exchange processes involving mono- and bis-adducts of phosphenium ions have received a theoretical treatment. The coordination chemistry of the carbene adduct (331) of the... 

A number of non-routine reactions of halogenophosphines are worthy of note. The first aliphatic phosphenium cation featuring a phosphorus-sulfur bond (17) has been obtained by treatment of the chlorophosphine (18) with aluminium trichloride in dichloromethane solution. A new synthesis of acyclic chiral t-phosphines has been developed which employs selective, sequential alkylation of the chloro(amino) phosphines (19) by Grignard and organolithium reagents. The key intermediates (19) are readily prepared by the... 

On the basis of structural variations in the hydridophosphorane it was previously suggested that the final step in this sequence was consistent with reversible formation of a sulfuranyl radical intermediate (43) followed by rate-determining sulfur-sulfur cleavage or a concerted process with a T.S. having a relatively high degree of phosphorus-sulfur bond formation . 

Bromodifliiorophosphine is also obtained by HBr cleavage of the phosphorus-oxygen bond of p.-oxobisdifluorophosphine 50), and there is one report of HCl cleavage of a phosphorus-sulfur bond 48)... 

Recently Martynov e< al. 179, 203) have synthesized some cyclic aminofluorophosphines containing phosphorus-oxygen or phosphorus-sulfur bonds by the following routes. 

Olefin synthesis starts usually from carbonyl compounds and carbanions with relatively electropositive, redox-active substituents mostly containing phosphorus, sulfur, or silicon. The carbanions add to the carbonyl group and the oxy anion attacks the oxidizable atom Y in-tramolecularly. The oxide Y—O" is then eliminated and a new C—C bond is formed. Such reactions take place because the formation of a Y—0 bond is thermodynamically favored and because Y is able to expand its coordination sphere and to raise its oxidation number. 

The remaining four elements form molecular solids. The atoms of white phosphorus, sulfur, and chlorine are strongly bonded into small molecules (formulas, P4, S8, and Cl2, respectively) but only weak attractions exist between the molecules. The properties are all appropriate to this description. Of course there is no simple trend in the properties since the molecular units are so different. 

While breaking of the carbon-to-phosphorus bond is a nuisance in catalysis with organometallic complexes, the breaking of carbon-to-nitrogen and -to-sulfur bonds is a desired reaction in the oil industry. Hydrodenitrification (HDN) and hydrodesulfurisation (HDS) are carried out on a large scale in order to remove nitrogen and sulfur from the fuel feedstocks. 

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