Tris bismuthine

There have been several reports of the formation of tertiary bismuthines by the action of free radicals on metallic bismuth. One method of generating the radicals iavolves cleavage of ethane or hexafluoroethane ia a radiofrequeacy glow discharge apparatus the radicals thus formed are allowed to oxidize the metal at — 196°C (53). Trimethylbismuthiae and tris(trifluoromethyl)bismuthine [5863-80-9], C BiF, have been obtained by this procedure. 

Other methods of preparing tertiary bismuthines have been used only to a limited extent. These methods iaclude the electrolysis of organometaUic compounds at a sacrificial bismuth anode (54), the reaction between a sodium—bismuth or potassium—bismuth alloy and an alkyl or aryl haUde (55), the thermal elimination of sulfur dioxide from tris(arenesulfiaato)bismuthines (56), and the iateraction of ketene and a ttis(dialkylainino)bismuthine (57). 

The reaction of tris(trifluoromethyl)bismuthine with chlorine, bromine, or iodine, however, has been found to yield the corresponding bismuth trihahde and trifluoromethyl hahde (61) ... 

Methyl bis(l-naphthyl)bismuthinate, Np.BiOCH,. The reagent is obtained in 80% yield by reaction of tris(l-naphthyl)bismuthine, Np3Bi, with chloramine-T in methanol. ... 

Methylpiperazine (217) and tris[spiro(l,3-benzodioxole-2,l -cyclohexan)-4-yl]bismuthine (218), prepared from the parent heterocycle by 4-lithiation and transmetalation (BuLi, Et20—THF, 24 h then BiCl3, 24 h 70%), gave l-methyl-4-[spiro(l,3-benzodioxole-2,l -cyclohexan)-4-yl]piperazine (219) [Cu(OAc)2, CH2C12, A, 20°C, 45 h 25%] several analogues likewise.1194... 

Tri-m-, tri-p-xylylarsine Triphenylstibine Tri-m-xylylstibine. Triphenyibismuthine Tri-p-tolyl-,tri- ct-naphthyl bismuthine, . ... 

Tris-or(/j< -lithiation of tris[2-(diethylsulfamoyl)phenyl]bismuthine with ferf-butyllithium followed by treatment with 3 equiv. of diaryliodobismuthine yields a branched tetrameric bismuthine, which, on similar treatment, leads to a dendrimer-type bismuthine [97CC2295],... 

A suspension of p-toluenediazonium salt-bismuth chloride complex (32.5 g) in cold acetone (100 ml) was treated with copper powder (52.8 g). An evolution of gas took place in several minutes and the solution became dark brown in color. After 1.5 h, an equal volume of 25% aqueous ammonia was added and the mixture was diluted to 450 ml with water. After standing for 1 h, the solid precipitate was filtered, dried, and extracted with dry chloroform. The extract was evaporated and the solid residue was crystallized from methanol to give tris(4-methylphe-nyl)bismuthine (3.07 g), m.p. 116-117°C [39JA3586]. 

Monomeric cyclopentadiene (10 g, 150 mmol) was added to a stirred solution of Bi(NMe2)j (9.00 g, 26.4 mmol) in absolute THF (60 ml) at -70°C. All manipulations need to be done in the dark. After 2 h, the mixture was allowed to warm to room temperature and was stirred for an additional 2 h. The mixture turned from deep purple to red, and a dark brown solid precipitated. The solution was filtered through Celite and the red colored filtrate was concentrated to about 6 ml, cooled to -30°C, and diluted with hexane (6 ml). After drying at 0°C in vacuo, tris(cyclo-pentadienyl)bismuthine was obtained as deep red, transparent crystals (7.40 g, 73.2%). The filtered brown solid was dried in vacuo to give (BiCsHs), as a brown, insoluble powder [95JOM(485)149]. 

A mixture of acryrlonitrile (24.8 g) and aqueous solution of 2N K2HPO4 (145 ml) was electrolyzed (0.5 A, 7 h) at 22°C in a divided cell with a bismuth cathode and a platinum anode. During electrolysis, 4.81 g of the anode was consumed. The organic layer of the solution in the anode compartment was separated and cooled to — 10°C, giving tris(2-cyanoethyl)bismuthine as white needles (8.22 g). The yields based on the current and electrode were 50 and 97%, respectively [74EL(10)1424],... 

Synthesis of tris 2-[7V -bis(2-hydroxyethyl)sulfamoyl]phenyl bismuthine... 

To a THF solution (15 ml) of tris 2-[MA -bis(2-tcrr-butyldimethylsiloxy)ethyl]sulfamoyl)phe-nyl)bismuthine (355 mg, 0.218 mmol) was added tetrabutylammonium fluoride (THF solution 1.35 ml, 1.35 mmol) at 0°C and the resulting mixture was stirred at room temperature for 3 h. Saturated aqueous NH4CI (15 ml) was added and the organic phase was removed by decantation. The aqueous phase was washed with ether (10 ml X 2) and then allowed to stand overnight. The deposit was filtered off, washed with water and recrystallized from 6% ethanol-water to yield tris 2-[/V,A -bis(2-hydroxyethyl)sulfamoyl]phenyl)bismuthine (125 mg, 61%), m.p. 202-204°C [98JCS(P1)2511]. 

It has been reported that highly hindered tris[2,4,6-tris(trifluoromethyl)phe-nyl]bismuthine is unstable in solution even under an inert atmosphere and, hence, found in the solid state when exposed to air, probably owing to the steric crowding around the bismuth atom [91JOM(402)55]. In contrast, tris(2,4,6-triphenylphenyl)bismuthine is a thermally stable solid with a definite melting point at 235°C [95JOM(485)141]. Based on the molecular... 

Bis(4-methylphenyl)bismuth A -(4-methylphenyl)sulfonylamide 4 is obtained in moderate yield by the reaction of tris(4-methylphenyl)bismuth [A -(4-methylphenyl)sulfonyl]imide with anise alcohol or cinnamyl alcohol [96JCR(S)24]. This amide is insoluble in benzene, but soluble in chloroform, and not so sensitive to oxygen md moisture in the solid state. However, it slowly decomposes to tris(4-methylphenyl)bismuthine and a white powdery deposit when the amide is stood in CDCI3. 

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