Other oxidations with sulfur and selenium

So, this fact is strong evidence in favor of the intra- and inter-molecular dative P—B bond in 126. In solution, 126 is easily oxidized and undergoes addition reactions with sulfur and selenium, with the formation of the corresponding oxide (166), sulfide (167), or selenide (168) [Eq. (129)]. The 3,P chemical shifts of other compounds (166) (27 ppm), (167) (47 ppm), and (168) (46 ppm) are close to that observed for their structural analogues. These data and the values of dipole moments of 4,3 and 4,5 D for 166 and 167, respectively, make it possible to exclude the formation of intramolecular dative P—B bonds similar to those observed for borylphosphine ethene... 

These trends are general ones, observed with other oxoadds of the nonmetals. Recall, for example, that nitric acid, HNO3 (oxid. no. N = +5), is a strong acid, completely ionized in water. In contrast, nitrous add, HN02 (oxid. no. N = +3), is a weak acid (Ka = 6.0 X 10-4). The electronegativity effect shows up with the strengths of the oxoadds of sulfur and selenium ... 

Phenylchalcogenyl-l-naphthols with sulfur (91), selenium (92), and tellurium (93) were prepared, as was the methylene analog (90), and their oxidation potentials determined by CV vs. SCE. All were irreversible, and only the Te compound 93 (1.00 V) differed significantly from the other three ( 1.25 V) (Table 9). It is likely that the naphthol moiety is controlling the oxidation potential of 90-92. Interestingly, only 93 showed significant ability to inhibit lipid peroxidation in a... 

Tellurium burns in air with a greenish-blue flame. The combustion product is dioxide, Te02, the most stable oxide of the metal. Tellurium also forms other oxides the monoxide, TeO, the trioxide, TeOs, and the pentoxide, Te205. Monoxide has not yet been obtained in solid form. Like sulfur and selenium, tellurium forms oxyacids. Such oxyacids include orthotelluric acid, HeTeOe and tellurous acid, H2Te03, in which the metal is in +6 and +4 valence states respectively. 

All the P-As and P=As bonded compounds are sensitive to hydrolysis and to oxidation by air. The reaction of Cp As=PMes with diazomethane adds a CH2 group across the double bond and yields the three-membered heterocyclic phosphaarsirane Cp AsCH2PMes. Sulfur and selenium add across the double bond to form three-membered heterocycles.Dimerization of Cp As=PCp produces two isomeric diphosphadiarsetanes, one containing the P-P-As-As and the other the P-As-P-As core. Photolysis of Cp As=PMes, Cp P=AsMes, and (2,4,6-r-Bu3C6H2)P=AsCp yields the diarsadiphosphacyclo-butanes. Metal complexes of several of the P=As compounds have been prepared and characterized. ... 

Binder and others [221, 222] proposed that the platinum surface should be modified with sulfur or selenium. The overpotential for oxidation of carbon monoxide and formic acid in sulfuric acid is reduced by 200 mV on the modified electrodes. Maximum activity is given by electrodes where the coverage with sulfur amounts to 0.3. 

Production and Economic Aspects. Thallium is obtained commercially as a by-product in the roasting of zinc, copper, and lead ores. The thallium is collected in the flue dust in the form of oxide or sulfate with other by-product metals, eg, cadmium, indium, germanium, selenium, and tellurium. The thallium content of the flue dust is low and further enrichment steps are required. If the thallium compounds present are soluble, ie, as oxides or sulfates, direct leaching with water or dilute acid separates them from the other insoluble metals. Otherwise, the thallium compound is solubilized with oxidizing roasts, by sulfatization, or by treatment with alkaU. The thallium precipitates from these solutions as thaUium(I) chloride [7791 -12-0]. Electrolysis of the thaUium(I) sulfate [7446-18-6] solution affords thallium metal in high purity (5,6). The sulfate solution must be acidified with sulfuric acid to avoid cathodic separation of zinc and anodic deposition of thaUium(III) oxide [1314-32-5]. The metal deposited on the cathode is removed, kneaded into lumps, and dried. It is then compressed into blocks, melted under hydrogen, and cast into sticks. 

---