Triphenylstibine oxide

Stevani and Baader attempted, unsuccessfully, to trap the volatile intermediate with triphenylantimony. Unfortunately, poly(triphenylstibine) oxide was formed instead of the expected insertion product, 2,2,2-triphenyl-2k -l,3,2-dioxastibolane-4,5-dione, probably by the reaction of triphenylantimony with hydrogen peroxide, carried by the gas stream to the flask containing triphenylantimony. Although it was impossible to detect the trapping product of 1,2-dioxetanedione by triphenylantimony, that does not necessarily mean that this substance is not formed during the reaction. This intermediate might... 

Triphenylstibine oxide. (CftH5).3Sb=0, reacts with dicyanoacetylene at room temperature, but no pure products could be isolated. Reaction with methyl propiolate at 115° gives methyl phenylpropiolate in 40% yield. 

The so-derived enthalpy of formation of gaseous triphenylarsine oxide, 261 18 kcalmol , just overlaps the value obtained from rotating bomb calorimetry, 227.6 +15.6 kJ mol . While related success arises in the comparison of the values for triphenylphosphine oxide we admit our discomfort with the large error bars accompanying all of these values. As such, while we derive an enthalpy of formation of triphenylstibine oxide using the static bomb results for stibine—and thus enter this value into Table 1—we regrettably consider it pointless even to compare the E—O bond enthalpies for the three triphenyl compounds. 

The deoxygenation of epoxides, sulfoxides, A-oxides, and triphenylarsine and triphenylstibine oxides at room temperature is also catalyzed by MTO with PPh3 as oxygen acceptor [26]. Again, a Re intermediate, containing the (ligand-stabilized) methyldioxorhenium, seems to be involved. A catalytic amount of MTO... 

Both trialkyl- and triarylstibine sulfides and selenides are known. Trimethylstibiae sulfide [15082-97-6], C3H9SSb, has been prepared from trimethylstibine oxide and hydrogen sulfide (164). It is monomeric in benzene and chloroform. Trialkylstibine sulfides and selenides have been prepared from tri-alkylstibines and sulfur or selenium, respectively (165). Unlike triphenylstibine oxide, the structure of triphenylstibine sulfide is tetrahedral, as shown by both Mu ssbauer and x-ray diffraction studies (153). A patent covering the synergistic use of triphenylstibine sulfide with aromatic amines as antioxidants in lubricating oils has been issued (166). 

Triphenylstibine oxide (PhaSbO) with the assistance of tetraphosphorus decasul-fide (P4S10) is a highly effective catalyst for the carbonylation of both amines and diamines with CO2 in the presence of 3 A molecular sieves, giving the corresponding linear and cyclic ureas in yields of 83-98% [777, 778]. 

Oxygen transfer to the metal site of several organometallics is also possible in some instances this occurred under ultrasonic conditions. In this way its polymeric oxide was obtained from triphenylbismuthine, whereas triphenylstibine afforded its crystalline dimeric oxide [57], Several metalloporphyrins are also oxygenated at the metal site by IOB. Some of the oxo species formed have been isolated but normally they are non-isolable. These systems have been used in some catalytic oxidations. 

Triphenyl phosphite, triphenylarsine, and triphenylstibine are not oxidized by NO (22). Because of the decreased basicity of these materials, the initial step in which BNO is formed probably does not occur, and as a result there is no oxidation. 

In 1960 triphenylstibonium methylide, Ph3Sb=CH2, was obtained in solution by treating methyltriphenylstibonium tetrafluoroborate with phenyllithium in ether When the resultant solution was treated with benzophenone, acid work-up provided high yields of triphenylstibine and diphenylacetaldehyde ", and it has been suggested that the latter product arose by acid-induced rearrangement of initially formed 1,1-diphenylethy-lene oxide, the most likely product from reaction of this reactive ylide with a carbonyl compound. 

Triphenylstibine diacetate, (C6H5)3Sb(OCOCH3)2. —Triphenyl-stibme in acetone solution is oxidised by 3 per cent, hydrogen peroxide and the oxidation product filtered off, dried and recrystallised from glacial acetic acid. The diacetate melts at 215° C., is readily soluble m warm methyl alcohol, and is converted to the corresponding dichloride by hydrochloric acid. 

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