Triphenylbismuthine

All three carboa—bismuth boads of trihen zylhismuthine [99715-52-3], C2 H2 Bi, (64) and triphenylbismuthine (65) can be cleaved by alkafl metals. Under some conditions, however, tertiary bismuthines react with sodium or potassium to yield secondary bismuthides. Thus a number of sodium dialkylbismuthides have been obtained by the iateraction of a trialkylbismuthine and sodium ia Hquid ammonia (66—69) ... 

At 100°C the tetraphenyl compound decomposes to triphenylbismuthine and metallic bismuth (68). 

Triphenylbismuth dichloride, 4 33 Triphenylbismuth difluoride, 4 27 Triphenylbismuth dimethacrylate, 4 33 Triphenylbismuthine, 4 26 Triphenylbismuth iodide isocyanate, 4 32 Triphenylbismuth iodide azide, 4 32 Triphenylbismuth oxide, 4 32 Triphenylcarbamate... 

It also occurs when triphenylbismuthine dichloride and potassium selenocyanate are shaken together for fifteen hours in light petroleum ... 

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. 

Scheme 8 demonstrates the synthesis of bis-mole-containing polymer 27 by the polymer reaction of diiodinated polymer 56. The reaction of the diiodobutadiene units of polymer 56 with Bu"Li generated lithiated polymer 57. This was followed by treatment with dibromophenylbismuthine. Dibromophenylbismuthine was prepared by the addition of triphenylbismuthine to 2 equiv of bismuth tribromide and was used without isolation (Scheme 8). 

Similar treatment of triiron dodecacarbonyl solutions with triphenylbismuthine and triphenylamine gives no isolable products. In the former case, the original green color of the solution is discharged in about 2 hours and an unidentifiable, brown, amorphous, uncrystallizable solid precipitates. In the latter case, a brown solid which contains no nitrogen is obtained. The triphenylamine is recovered unchanged. 

We now turn to the three PhsE species. The directly measured, combustion-derived, enthalpies of formation of triphenylarsine, triphenylstibine and triphenylbismuthine increase in the order As < Sb < Bi as do the parent trihydrides and our derived values for the trialkyl species. However, we will not attempt to make any further comparison between the enthalpies of formation of the three triphenyl species or between them and the trihydrides and/or trialkyls. In the absence of rotating bomb calorimetric results for triphenylstibine and for all of the trialkyl species, values are too inexact to warrant any further discussion. ... 

Bismuth. Heat for 10 minutes at 250° C. in hydrogen atmosphere. Triphenylbismuthine. Hilpert and Grlittner, Ren, 1913, 46, 1675. 

Bismuth tri-lu oinide. Dry etlior solution. Triphenylbismuthine. Challenger and Allpress, Trans, Gkem. Roc., 1921, 119, 913. 

To a stirred suspension of triphenylbismuth dichloride (2.56 g, 5 mmol) in 95% ethanol (60 ml) was added hydrazine hydrate (2.0 g). Reduction occurred immediately. The solution was decolorized and triphenylbismuthine precipitated out of solution. Stirring was continued for 1 h and then the mixture was poured into water (300 ml). The aqueous suspension was extracted with ether, the organic layer was separated and dried, and the solvent was removed to give the product (2.1 g, 95.4%), m.p. 75-76°C [40JA665]. 

Via dismutation (method O) Mixed alkyl(perfluoroalkyl)bis-muthines are obtained from the dismutation reaction between trialkylbismuthines and perfluoroalkyl iodides (Rfl) [63AJC636]. Cyanodiphenyl-bismuthine is formed by the reaction of triphenylbismuthine and iodonitrile [15JCS(107)16],... 

Metal coordination (method Q) Reaction of triphenylbismuthine with triamminechromium tricarbonyl in dioxane at 120°C leads to a mixture of chromium tricarbonyl ir-complexes of triphenylbismuthine [81IZV1874], Extraction and recrystallization permit separation of three types of bismuthine. 

A mixture of triphenylbismuthine (4.4 g, 10 mmol), triamminechromium tricarbonyl (5.7 g, 30 mmol), and dioxane (40 ml) was heated with stirring for 7 h. After separation of the calculated amount of ammonia, the cooled mixture was filtered, the clear yellow solution was evaporated in vacuo, and the residue was treated with hot hexane. The solution was decanted and the residue was dried in vacuo. Extraction with hot cyclohexane yielded yellow crystals (0.73 g) soluble in benzene and acetone. After recrystallization from ethanol, I was obtained. Extraction with hot benzene of a portion of the product, after the separation of I, yielded a yellow compound (3.05 g), which was recrystallized from benzene to give II. Recrystallization of the residue from dioxane gave III (2.62 g) [81IZV1874]. 

The dipole moment of triphenylbismuthine is reported to be essentially zero in benzene, cyclohexane and octane, suggesting that either each Ph-Bi group is effectively non-polar or that the resultant moments of three Ph-Bi bonds are compensated by the moment of the lone pair [32ZPCB401, 63JCS1739, 41JOC421]. The dipole moments observed for tris(4-methylphenyl)bis-... 

Trimethylbismuthine exhibits broad absorptions at Xmax 211.5, 222.5 and 260.0 nm in the far-UV region [71JA822]. Triphenylbismuthine shows characteristic absorptions at 248 and 280 nm. There have been several interpretations for its UV spectrum the interpretation most likely to be accepted is that the shoulder at 280 nm is due to the tt-tt transition of benzene, and the... 

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