Bismuth and Bismuth Alloys

BISMUTH AND BISMUTH ALLOYS
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The element bismuth /7440-69-97, Bi, found in Group 15 (V A) of the Periodic 'fable, has at no. 83, at wt 208.98. Its valences are +5 and +3. Bismuth is a silvery metal having a high metallic luster and exhibits a slighdy pink tinge on a cleanly broken surface. The metal itself is brittle in nature and easily broken.

Georgius Agricola, a German scientist of the sixteenth century. was the first to mention bismuth detailing the melting of bismuth from ore (1). It was in the sixteenth century that bismuth compounds were first discovered to have a soothing effect on stomach disorders. Bismuth compounds are still widely used in preparations to relieve this condition. Not until the 1800s was bismuth refined and proven to be an clement. Lntil that time, bismuth was usually referred to as nne of the other elements with which it is associated in ores such as antimony, silve-r, lead, and tin.

Occurrence

Bismuth is referred to as a minor metal. IL is not generally ruined [or its own intrinsic value, rather it is ruined primarily as a by-product of lead or copper ores. In China, however, bismuth can be found in tungsten ores. Ill. Bolivia the metal has been mined for its own value, but this has not happened on a consistent basis over the years because fluctuations in the bismuth price have at tim.es made it uneconomical to recover.

Bismuth occurs in the earth's crust in a concentration of approximately 0.1 ppln on the average. IIigher concentrations of bismuth occur in oceanic manganese nodules in a range of 0.5 to 24 ppm (see OCbllJ'.I_v~\>/ .lv1.AT.l::l}:_.A...LS). The next highest concentration of bismuth is found in silicic rock at 0.02 to o. I) ppm (2).

Properties

The physical properties of bisrnuth, summarized in Table 1, are characterized by a low IllelLing point, a high density, and expansion on solidification. Thermochemical and thermodynamic data are summ.arized in Table 2. 'I he solid metal floats on the liquid metal as ice floating on water. Gallium and antimony are the only other metals that expand on solidification. Bismuth is the rno st diarnagnetic of the metals, and it is a poor electrical conductor, The thermal conductivity of bismuth is lower than that of any other metal except lllercury.

Table 1. l'hysicall'roperties of Bismuth

Pro ertv

Value

1.560 0.309

hp,OC

Ri-Ri bond length at 25°C, nm crystal ionic radius, nm

Ri-

BiH

Bi:::;+

crystal structure density, kg/ mj 200e

271°C"

271°Cb

6000e

electrical resistivity, Ovcm o-c

200e

expansion on freezing, by vol

hardness, Mohs' scale

magnetic susceptibility

solid

liquid

mp,oC

vapor pressure, kPa~ 4000e

6000e

8800e

14200e

viscosity, mPa·s( cP) 285°e

30re

365°(:

4s1°e

600°(:

0.098 0.096 0.074

rhombohedral

9,800 9,740 10,070 9,660

106 X 10-' 120 X 10-'

3.3 2.5

-280, 10 12

-10.5 X 10- ,'.

271.3

1.013 X 10 4 1.013 X 10 1 t.oia e to- 1.0n X 10-

1.610 1.662 1.460 1.280 0.998

"Solid.

b Liquid.

c . 1'0 convert kl'a to psi, divide by 6.89.5 X 103 .

Table 2. Thermochemical and Thermodynamic Properties of Bismuth

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

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Value

56.9

entropy at298 K, AI)°, J/(mol·Kr entropy of transition, DoS, J /(mol·EY solid

liquid

heat capacity, My J /(kg.J<)' -173.15°C

25°C

25-271°C

271-1027°C'

heat of fusion, ~iiJ' k! /kgd heat of transjtion, /\T1,J/11101:1 solid

liquid

heat of vaporization, ~vay kJ /kg a thermal conductivity, W /(m·K)

20.2 90.4

108

122

4.49-.5.40 X 10-3 T C 235'

51.816

11.0 172 858.29

Temperature

parallel to triagonal axis perpendicular: to triagonal axis polycrystalliue

thermal expansion coefficient 20-100°C

5.54 9.53 8.22

(13.4 x 10 ')/K

5.30 9.19 7.92

4.81 8.44

7.22

3 To convert from J to cal, divide by 4.184. b Temperature ill degrees kelvin.

CLiquid.

d Units are J!(mo]·K). '1'0 convert from] to cal, divide by4.1S4.

Production

Bismuth is mined primarily as a by-product of the processing of ores of other metals, mostly copper and lead. The countries that mine significant quantities ofbismuth are Australia, Bolivia, Canada, China, Japan, Mexico, Peru, and the United States. Production is summarized in Table 3.

Table 3. Annual Bismuth Production, r"

Year

\Xlor1d lToductionl.

1986

1987

1988

1989

1990

35% 4082

mine

%58 4077

3(73 4078

3220

3200' 3710'

refinery

4098

a Ref. 3.

b Excluding the Lnited States. C Rsrirnated.

Tn Australia, bismuth is mined as a by-product of copper ores by Peko-Wallsend Ltd. and exporterl for refining. Bolivia. is the only counhy in the world where concentrations of bismuth are high enough that it is mined for its own value. The 'Lasna mine in Bolivia is thus unique. This mine was shut down for most of the 1980s, howe-ve-r, because the Iree-rnarket price [or bismuth dropped to a low value in the late 1970s and remained low lhrough the early 1980s.

Mined bismuth in China is a by-product of lungs len Illining operations, but rno st of the bismuth produced in China cornes from bismuth concentrates.

The principal portion of the bismuth in copper (qv) orcs follows the copper into the matte. During the conversion of the matte to blister copper rno st of the bismuth fumes off. TIle fumes are caught.in the baghouse or Cottrell svetem along with other elements such as lead (qv), arsenic, and antimony. These dusts are transferred to the lead-smelting operation. The portion of the bismuth remaining with the blister copper is separated during the electrolytic refuting in the slimes. The procedure for handling the slimes results in the bismuth be.ing collected in the lead bullion (4).

The bismuth that is found in the lead ore accompanies the lead through the smelting operation right up to the last refining steps. The removal of bismuth then requires special techniques, the most common heing the Betterton-Kroll and the Betts processes (5).

Betterton-Kroll Process. Metallic calcium and magnesium are added to the lead bullion in a melt and form ternary compounds that melt higher than lead and are lower in density. By cooling the lead bath to a temperature close to the melting point of lead, the intermetallic compounds high in bismuth content solidify and float to the top where they arc removed by skimming.

TIlls bisrnu th+calciurn-nnagnesium dross also contains lead that rnust he removed. TIle dross is healed in a kettle to free any entrapped lead that melts and forms a pool under the dross. This lead is cast and returned to the bismuth separation cycle. The dross is then melted and treated with chlorine and/ or lead chloride to remove the calcium and magnesium. The resulting molten metal is an alloy of bismuth and lead, high in bismuth which is then treated to produce refined bismuth metal.

lletts Electrolytic Process. TIle Bells process starts with lead bullion, which Inay carry lin, silver, gold, bismuth, copper_, antimony, arsenic,

selenium, tellurium, and other impurities, but should contain at least 90% lead If more than 0.01 ~/O tin is present, it is usually removed from the

bullion first by rneans of a tin-drossing operation (see TIle lead bullion is cast as plates or anodes, and tuunerous anodes are

set III parallel III each electrolytic cell. Between the anodes, thin sheets of pure lead are hung from conductor bars to form the cathodes. Several cells are connected in series.

The electrolyte is a solution of lead fluosilicate [25808-74-6], PbSiF(l' and fluosilicic acid {16961-834], H:zSiF G' containing a small amount of glue or other suitable agent. Direct current is passed through the cells to dissolve the lead from the anodes and deposit it on the cathodes. The impurities in the lead anodes are insoluble under the condir.ions of normal cell operation awl remain on the face of the anodes as a porOllS slime blanket. The finished cathodes are withdrawn form the cells, washed, and melted to refined lead. 'Lhe scrap anodes are withdrawn, and the slime is washed free of soluble matter, either while still on the anode or after it has been removed by cleaning. TIle cleaned anode scrap is returned to the anode-cas ling kettle [or recastinjz.


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TIle washed slime is dried and melted to produce slag and IueUJ. The slag is usually purified by selective reduction and smelted to produce antimonial lead. The metal is treated in the molten state by selective oxidation for the removal of arsenic, antimony, and some of the lead. It is then transferred to a cupel furnace, where the oxidation is continued until only the silver-gold alloy (doni) remains. The bismuth-rich cupel slags are crushed, mixed with a small amonnt of sulfur, and reduced with carbon to a copper matte and impure his.rnuth metal; the latter is transferred to the hisrnuth refining plant.

111f' gasps from the several furnaces treating the slimes carry bismuth, silver, gold, and othervalues as particulates, which are recovered via Cottrell precipitators, baghouses, or scrubbers.

Recovery of Bism urh fr01TI Tin Concentrates. Bismuth is leached from roasted tin concentrates and other bismuth-hearing materials hy tneans of hvdror-hloric acid. TIIP acid leach liquor is clarifie-d hy spUling or filr rarion, and the bisrruuh is precipitate-d as hisrruuh oxychloride L7787-S9-9], BiOc:1, when the liquors are diluted using large volumes of water. TIle impure bismuth oxychloride is nsually rerlissolverl in hydrochloric acid and reprecipitated by diluting several times. It is then dried, mixed with soda ash and carbon, and .reduced to metal. The wet bismuth oxychloride lTIay also be reduced to metal by means of iron or zinc in the presence of hydrochloric acid. '1 he metallic bismuth produced by the oxychloride method requires additional refining.

TIle Sperry process for IIlaking white lead in an electrolytic cell recovers bismuth as a by-product in the anode slimes.

The crystallization process for concentrating bismuth in lead by squeezing the eutectic (high in bismuth) liquid out of the solidified high lead portion at a LelIlpe:raLure within the 1uelting range of the alloy is seldom used.

Refining. The alloy of bismuth and lead from the separation procedures is treated with molten caustic soda to remove traces of such acidic elements as arsenic and tellurium (4). It is then subjected to the Parkes desilverization process to remove the silver and gold present. 'Lhis process is also used to remove these elements from lead.

TIle desilverized alloy now contains bismuth as well as lead and zinc. To rern.ove the lead and zinc, advantage is taken of the fact that zinc and lead chlorides are formed before bismuth chloride /7787-60-2}, BiCI3, when the alloy is treated at 500°C with chlorine gas. Zinc chloride 17646-85-7}, ZnCi" forms first, and after its removnl lead chloride [775R-9S-4_7, PbCl2, forms preferentially. 'This process is continued until the desired level of lead removal has been reached. TIle hismuth is given a final oxidation with air and caustic soda; the refined product has a purity of 99. 999%).

Fabrication. There arc four basic forms of bismuth that are readily available commercially ingot, needle, pellet, and powder. Bismuth ingots range from 4.5 to 13.6 kg each depending on the producer. Ingots are used mostly in metallurgical additives and in making fusible alloys. Bismuth needle is typically 0.16 CIII (0.0625 in.) in diameter hy nominally 2.54 CIU in length. Needle is used primarily in the production of bismuth compounds [or 'pharmaceutical and catalyst applications. Bismuth powder is produced in varying mesh sizes [or the electronics industry.

Bismuth pellets range from 4.5 to 60 g in size and are used for metallurgical additives. Their convenient size and specific weights make them particularly useful as feedstock when a given quantity of bismuth must be added regularly to a melt.

Economic Aspects

The United States is highly dependent on bismuth imports because domestic usage grearly outruns domestic production. In 1990, the United States imported 16·12 t ofhismuth (3). 111e primary sourc-es ,ITe Belgium, Mexic-o, and Peru. Snbsraurial quantities of metal were also imported from Canada, China, Germany, and the United Kingdom. i\. small quantity of bismuth was imposed from Japan.

111e supply of bismuth metal, is dependent on the supply of the associated metals with which it is mined. Since the 1970s bismuth prices have ranged from less than $4.4D/kg to over $44!kg because of supply and demand. The price reached an all time high of over $44!kg in May of 1974 and fell to an all time low of under $3.30/kg in the summer of 1982. Bismuth finished off 1990 at $6.17-6.39/kg (8).

Uses

The three primary categories of uses of bismuth in industry, chemical, metallurgical additive, and fusible alloy, and the respective quantities, are given in Table 4. The chemical catcgory can be broken down into pharmaceuticals, cosmetics, catalysts, industrial pigments, and electronics; the metallurgical additive category into steel, aluminum, and cast-iron additives. The fusible alloy category is divisible into more than a dozen subcategories dependent on specific application.

Table 4. Annual United States Consumption of Bismuth Metal, ta

Year
Use 1986 1987 1988 1989 1990
chemicals b 663 748 619 659 50
fusible alloys 290 334 332 272 249
metallurgical additives 350 494 493 396 424
otherc 21 21 27 25 24
TOla? 1324 1597 1531 1352 1274 'Ref. 3.

b Includes industrial and labo.ratory chemicals, cosmetics, and pharmaceuticals. c Includes other alloys and experirnental uses.

dData 111ay not add to totals shown because of independent rounding.

Until 1930, approximately 90% of bismuth usage was for pharmaceutical applications (9). From that point until the 1970s, research produced new applications that greatly expanded the uses of the metal. At that point the pharmaceurical use accounted for ahont SO~iO of the total bismuth consumption. By 1991, the fusible alloy category along with the other subdivisions each accounted for about 10% of the bismuth usage. Pharmaceutical usage was down to 20n/~

As a metallurgical additive, bismuth is used in the manufacturing of free-machining steel and free-machining aluminum. Bismuth is added in pellet, granule, or shot form into the pouring stream during filling of the ingot mold. The amount of bismuth added can range from 0.003-0.10% depending on the type of steel. The bismuth addition enhances the action of lead in the steel by producing less frictional resistance at the cutting edge of the tool. TIlls produces thinner and smaller chips, higher productivity, and better surface finish.

Bismuth Alloys

Because bismuth expands on solidification and because it alloys with certain other metals to give low melting point alloys, bismuth is particularly well suited for a number of uses. _Alloys of bisrnuth can be made that expand, shrink, or remain dimensionally stable on solidification. All other metals except galliUIll a.nd antimony contract on solidification. Bismuth alloys and uses are summarized in Table 5.

Tahle 5. Alloy Compositions and Uses


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Com osition, wt %
Melting point, Bismuth Lead Tin Cadmium Indium Antimony Lscs a
°C
47 44.7 22.6 8.3 5.3 19.1 0.0 LB
58 49.0 18.0 12.0 10.0 21.0 0.0 1.15
70 50.0 26.37 13.3 10.0 0.0 0.0 RS, W,LB
101 39.4 29.8 30.8 0.0 0.0 0.0 FSD
124 55.5 44.5 0.0 0.0 0.0 0.0 PC
138 58.0 0.0 42.0 0.0 0.0 0.0 W,SMF,FC
138/170 40.0 0.0 60.0 0.0 0.0 0.0 IC n LD = lens blocking; ,V = work holding, TIS = ra.dia.tion shielding; rSD = fusible safety device; PC = proof casting; Sl\1F = sheet metal forming; Fe _ fusible cores; lC - investment casting.

Uses of Alloys.

Anchoring. Bismuth alloys that expand 011 solidification are particularly useful [01 aligning and selting punches in a die plate. It is much easier to melt and POUI an alloy around a punch than to machine the entire die plate and punch at the sarne tune. TIlls method also makes it easier to relocate parls OI: change dies. TIle low teIllperatuH::'s involved do not cause distortion.

Radiation Shielding. Like lead, bismuth absorbs radiation. Therefore, bismuth alloys are widely used in the medical industry during radiation therapy. 'Lhe alloy is molded to the shape of various organs that are to be shielded. 'Lhen the molds are placed between the radiation source and the patient to protect the patient's vital organs from radiation exposure.

Electromagnetic and Radiofrequency Shielding. Because bismuth is highly diamagnetic, its alloys are quite useful in applications where electronic equipment must be protected from outside interference or where equipment can cause outside interference.

Tube Bending. The search for high strength, low weight structural materials produced the use of hollow tubes of many metals and alloys as structural components. These materials must often be bent and shaped to fit. Bending an empty tube causes distortion of the shape of the tube by flattening or wrinkling. These tubes can he filled with u low luelting bismuth alloy that allows the tube to he bent as if it were solid, thus elitninatinjz distention. 111en the alloy can he easily melted our of the tube and reused.

Fusible Safety Devices. Low melting bismuth alloys, especially those that are eutectic have found numerous uses in safety devices. These alloys can be cast into any shape necessary in order to be used in a plug or switch that must function at a given temperature.

Lens Blocking. Bismuth alloys have become particularly useful in the optical industry for securing lenses for grinding processes. TIle low melting point prov-ides that the lenses Inay be secured without preheating. The alloys have high strength so that good control is maintained during the grinding p.rocess. These alloys then are easily removed by melting in hot water and then reused.

Fusible Cores. TIle use of low luelting bismuth alloys has made it possible to produce items having complex internal cavities that cannot be produced using conventional core molds. These alloys arc dimensionally stable so that when they arc cast they result in a core piece having the most exact detail and surface finish required. These alloys are being used in the electro[olluing industry as well as the plastics industry where cost and weighL reduction have become critical. Once molding or electrofonuing is complete the part is immersed in a heat bath that ruelts out the alloy for reuse.

Steel Quenching. Bismuth and bismuth-dead alloys are used in the processing of some steel products. The thermal conductiv-ity of bismuth makes it ideal for use in quenching steel. The use of a bismuth-lead alloy in place of lead alone has the advantage of lowering the operating temperature of the bath as well as reducing adherence of alloy to the steel.

Pl'OofCastillg of Dies and Molds. Low luelLing alloys make the process of dielllalung faster and easier. TIle low Lelllperature alloys can he cast into a mold paLtelIl at virtually any point in the manufacturing process without long delays in production and without the possibility of heat dis tortion. These alloys produce a casting that is exact in detail, requires no curing time, and is completely reusuble.

Work Holding and Work Supporting. Low melting bismuth alloys have been used to solve two problems in machining operations. First, these alloys are used to hold parts that need machining but have no regular side that can be clamped. Second, bismuth alloys provide a method of support for parts such as turbine blades that are not stiff enough to stand alone for machining.

Sheet Metal Forming Dies. Engineers have found that low melting alloys, because they are tough and durable, are suitable for making castings that produce hundreds of pres sings in sheet metal of normal materials from aluminum to titanium. Once a given short run of pres sings is complete, the tooling can easily be melted and used for another tooling job.

Safety No ind u strial poisoning [r:01U bismu th has been reported (10). Howeve-r, pr:ecau Lions should he taken agains L the careless handling of bismuth and its compounds; ingestion and inhalation of dusts and fumes should he avoided.

BIBLIOGRAPHY

"Bismuth and Bismuth Alloys" in RCTlst ed., Vol. 2, pp. 526-.133, hy \X/. C Smith, Cerro de Pasco Copper Co.; in ~CT2nd ed., Vol. 3, pp. 527-535, hy H. E. Howe, American Smelting and Refining Co.; in ECT3rd ed., Vol. 3, pp. 912-921, by S. C. Carapella.]r. and H. E. Howe, American Smelting and Refining Co.

1. B. Dibner, _AgriCOk1 onMetals, Bumdy Library, K orwalk, Coun., 1958, p. 41.

2. J. \Xi. Hasler, 11. H. Miller, and R. 11. Chapman, United States AlineraJ Resources, Geological Survey Professional Paper 820, U.S. Department of the

Interior, \\lashington, D.C., 1973, p. 96.

3. ....Vlineral I1tdHstry S urvrys, Bismuth AJ111Ual Review, u.s. Bureau of IvLines, Washington, D. c., 1990.

4. A. R. Powell, in papm of/he Imli/ute ofAIining andiHe/alhllXY SymposiuJJJ, Institute of Mining and Metallurgy, London, UK, 1950, pp. 245-257.

5. J. O. Betterton and Y. E. Levebeff }v[e/allutgy of Lead and Zinc, American Institute of-"1ining and Metallurgy Engineers, New York, 1936.

6. P. M. Gruzensky and W. J. Crawford, U.S. BUI: Mines Inf Cir«, 7681 (1954).

7 F Vogel, Metalillerlin 21(2),122 (1967)

8. o. Abrams, NletaJs lf7eek, lvIcGraw-Hill, Inc., New York, Dec. 31, 1990, p. 5.

9. J. 11. Carlin,]l"., kfineraIFact.! and Pmblem.f, ns. Bureau of Mines, \N'ashington, D.C,1985, p. 1.

10. ~. 1. Sax, Danp,erolls Troperties of Industrial AI ate rials, 4th ed., Van X osrrand Reinhold Co., Ivew York, 1975, p. 459.

General References

R. C \\least, ed., CRC T landhoale q/Cbemi.ft1)' and Pl!J.fil~\, 71 st ed., CRC Press, Boca Raton, na., I 991.

L. G. Stevens and C. E. T. Wbite, '1 he Metals Handbook, Vol. 2, 10d, ed., ASM International, 1990, pp. 750-757.

MarkJ. Chagnon Mctalspccialtics, Inc.


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BISMUTH COMPOUNDS

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BISMUTH COMPOUNDS

Bismuth is the fifth member of the nitrogen family of elements and, like its COllgf'Tlf'l'S, possesses five electrons in its outerruo sf shell, 6/6p-). Tn many compounds, the bismuth atom utilizes only the three 6p electrons in bond formation and retains the two 6s electrons as an inert pair. Compounds are also known where bismuth is bonded to four, five, or six other atorns. Many bismuth cornpound s do not have simple molecular structures and exist in the solid state as polymeric chains or sheets.

TIle -3 oxidation state is exhibited by bismuth ill the vast majority of its compounds. A few inorganic and a variety of organic compounds, however, contain the element in the -5 state. Other rarer oxidation states reported for bismuth include -2, + 1, and -3. Bismuth also forms polynuclear ionic species with oxidation states that are usually fractional and range from 1 to I 1.

Technical information concerning bismuth and its compounds is distributed periodically by the Bismuth Institute, a nonprofit organization incorporated in La Paz, Bolivia, that has an information center in Brussels.

The United States consumed 1500 metric tons ofbismuth in 1988 and exported 147 t (1). The average domestic dealer price was $12.74/kg. The world mine output, excluding the United States, was estimated to be 2770 t in 1988; the world refinery production was estimated as 3510 t. Of the bismuth consumed in the United States, 679 t was used for industrial and laboratory chemicals, cosmetics ('1y), and phrrrmacenticals ('1"-); 133 t for fusible alloys; 493 t for metallurgical additives; 12 t for other alloys; and 15 t for miscellaneous purposes.

Analysis

Many of the methods used for the determination of bismuth are not very selective; thus it is often necessary to separate it from interfering substances. A gravirnetric method for the determination of bismuth in drugs, in the absence oflead, is described in considerable detail (2). A polarographic method for bismuth in dIUgS is also described in the same volume. TIw direct titration of bismuth, using the disodiurn salt of erhvlenerliarnineretraaceric acid (FDTA), has been found to be the best general method for determining macro and scmimicro quantities of bismuth (3). The method is fast, convenient, and accurate. Pew foreign ions in moderate amounts interfere. TIle titration is best carried out at a pH between 1.5 and 2.0. When the end point is detected by photometric methods, the titration of bismuth as dilute as 10-e molar is feasible. Several photometric methods have been described for determining trace amouru.s ofbismuth in (moo's or in nonferrous alloys using l't-'agt-'nls such as dithizone-, Lhiourea, potassium io(li(lt-', or dimercaptothiopyrone (4). Differeurial anodic stripping volrarrrmetry has also been used for the dererrninntion of small amounts (5 J.lg/L) of bismuth (.1).

For the determination of trace am..ounts of bismuth, atomic absorption spectrometry is probably the most sensitive method. A procedure involving the generation of hisrnuthine hy the use of sodium horohvdride followed hy flarneless atomic ab sorption spectromehy has been desc-ribed (6). TIw sensitivity of this method is given as 10 pg/0.0044./1, where A is an absorbance unit; the precision is 6.7S/O for 25 pg of bismuth. The low neutron cross section of hisrnuth virtually rules out any determination of bismuth based on neutron absorption or neutron activation.

Inorganic Compounds of Bismuth

llismuthine. Bisrnuthine [18288-22-7], Bill}, is a colorless gas, unstable at roorn teIIlperature, but isola table as a colorless liquid at lower temperatures. Owing to its instability and difficulty of preparation, no more than a few hundred milligrams of the pure compound have been available for any single study. Vapor-pressure data from -116 to 43L C have been determined, and by extrapolation, a normal boiling point of 16.8L C has been inclicaled; liHv.' calculated from the same data, is 25.15 kJ/nlOl (6.01 kC~J/IIlOI) (7).

'1 he existence of bismuthine was first demonstrated by using a radioactive tracer, 212 Bi (8). Acid treatment of a magnesium plate coated with 212 Bi resulted in the liberation of a volatile radioactive conrpountl. In subsequent experiments, tnajznesiurn bisrruuhide [1204846-3], lvlg?B~., was treated with acid: the yield, howeve-r, was only one part of hisruuthine for every 20,000 parts of hisrnuth dissolved. Attempts to prepare bisrnuthine by reduction of bismuth trichloride with a borohydride have not been particularly successful. Experimental quantities are best prepared by dispropcrtionation of either methylbisruuthine [66172-95-0), CHsBi, or dimethvlbisrnuthine [14381454], C2HjBi (7):

In the case or methylhisrnurhine, the disproportionatiou OCCU1"S llponlwt-'ping the compound (II -15°C f01" se-veral hours; 389.'1 TT1g of ruef hyllusmuthine yields 241.1 mg of Bil-L.

At room temperature bismuthine rapidly decomposes into its elements. The rate of decomposition increases markedly at higher temperatures (S).

Bismuthine decorrrposes when bubbled through silver nitrate or alkali solutions hut is unaffected hy light, hydrogen sulfide, or 4 N sulfuric acid solution. There is no evidence for the forrnntion of Bil-l " 4' though the phenyl derivative, (C(\H.')4TIi+, is known. TIle existence of Bil-l" 4 would not be anticipated on the basis of the trend found with other Group 13 (V) "onium' ions.

Bism uthides. Many intcrmctallic compounds of bismuth with alkali metals and alkaline earth metals have the expected formulas ~vI::Bi and lvI3B~, respectively. These compounds are not saltlike but have high coordination numbers, interatomic distances similar to those found til. metals, and metallic electrical conductivities. TIley dissolve to scune extent in molten salts (eg., NaCI-N a1) to form solutions that have been interpreted [rOl11 cryoscopic data as containing some Bi3-;. Both the alkali and alkaline earth metals fonn another series of alloylike bismuth compounds that become superconducting at low temperatures (fable 1). 'Lhe ..l\lB~ compounds are particularly noteworthy as having extremely short bond distances between the alkali metal atoms.

Table 1. Alloylike Superconducting Bismuth Compounds

Compound

FOIIIlula

CAS Registry Number

Temp, K

lithium bismuthide sodium his.rnuthide potassium dihismuthide rubidium dibismuthide

! 12048-27-0j [I 225f1-IiJ-fl] [124JI-17-J] [,)5127-10-1] [I 22JJ-24-fl] [66271-894] [12589-81-0]

Lilli NaBi KTIi') RbBi, CsTIL, CaBiJ SrBi~

2.47 2.22 3.SR 4.25

cesium dihisrnuth ide

4.75

calcium tribismuthide

1.7 5.62

strontium tribisrnuthide


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BISMUTH COMPOUNDS

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barium tribisrnu thide

[12047-02-8j

BaBi)

5.69

a Temperature below which the compound is superconducting.

B ism uth IIalides. TIle bismuth trihalides are the best known. Bismuth does form a single pentahalide, BlP 5' and subhalides that approximate the composition BjX_, the best characterized of these being BiOU6T Vapors above solutions of a bismuth trihalide in molten bismuth contain the species BiX and/ or (BiX)fi' where X = 0, Br, or I (9). At temperatures below 323°C, a black, diamagnetic. orthorhombic solid of the overall composition BiCL may he isolated from s.olution s of hismuth trichloride in molten hisrnuth (10).

Direct halogenation of metallic bismuth yields bismuth pentafluoride in the case of fluorine, the corresponding bismuth trihalides for the other halogens. Reaction of hismuth trioxide with aqueous HII', HCl, or HEr yields the corresponding bismuth trihalide. Physical and thenncchemical properties of the more important bismuth halides appear in Table 2.

Table 2. l'hysicall'roperties of Bismuth Compounds

Bismuth CAS Form M Bp. LHJ:,29S' S~'98 ' ,6,IIjCu£lO::l ' ~SfuOlo'n ' !'.H ou'ol !:c.S'
subl,:::9S'
compound Regislry ula P, °C kJ/nlol~ J/moiK kj/mol J/mol-K kJ/mol" J/mol.I(~
Xumber °e 11i- X Reteren

bund

energy, kT/mol'"

900± 13

123_ 4

Jl.6 0,6

23.4± O.S

201 _.:>

195 ± 3

BiF., 64 900 [0
9b
BiFs 15 230
I
BiCI3 23 44.7
3.5
BiCl bismuth [7787-61-
trifluoride »
bismuth [7787-62-
pentatluorid 4/
bismuth [7787-60-
trichloride ?'
-j
bismuth [14899-7
monochlori 0-8]
de
hisnmth [77R7-59-
oxychloride 9_7
bismuth /7787-58-
tribromide fI'
-j
bismuth [7787-64-
triiodide 67
bismuth ! /304-76-
trioxide 3j
bismuth [1345-07-
trisulfide 9)
bismuth [13()U2-
tritelluride 17 381

12

-~79

18~± 2

23.9

13,14

-I'll

'100+ 4

94.5

13,15

n.oc -367 120 13
I
Billr3 21 441 -27e± 2 190= 1 21.8 115 = 1 182 ± 1 ?~~.O + 1.4 16
9
BiIj 40 542C lfll +4 221,8 ± 0.8 )8,I=U,) 57.:) ± U.·1 134.3 ± 0,5 183.4 ± 0,8 181 ± 5 17,18
8.6
B;,°3 82 -,17-1 151.5 13
4
Bi,S 85 -143 200 13
0
Ri,Te 77.4 260.9 13 u To convert T to cal, divide bv 4.184.

b 'Lhe mp fre~uently cited is ~20°C higher than this and is, apparently, for material contaminated with oxy±luoride. C The normal bp has been extrapolated from vapor-pressure data.

d Monoclinic.

Bismuth Trifluoride. Bismuth(III) fluoride is a white to grey-white powder, density 8.3 g/ mL, that is essentially isomorphous with orthorhombic YF3, requiring nine-coordination about the bismuth (11). It has been suggested that BiF3 is best considered an eight-coordinate structure with the deviation from the YF.3 structure resulting from stereochemical activity of the bismuth lone-pair electrons. In accord with its structure, the compound is the most ionic of the bismuth halides. It is almost insoluble in water (.j.03 _ 0.05 10-3 j_1J at pH 1.15) and dissolves only to the extent of 0.010 g per 100 g of anhydrous HF at 12.4°C_

Bisrnurh trifluoride is usually prepared by dissolving either TIi::;O_') or TIiOP in hydrofluoric acid to yield the addition compound bismuth trifluoride trihydroflnorirle [661154-11-0], TIir') -3HP or H_')(BiP1) Careful evaporation of the solution permits isolation of a grey solid, which upon heating loses HP to yield BiF,. It may be purified by sublimation in a stream ofHF at 500°C. Bismuth trifluoride may also be prepared by direct fluorination of bismuth by: (1) reaction of Biz03 with sulfur tetrafluoride, SF'1; (2) treatment of metallic bismuth with IIF at 350°C; and (3) reduction of BlF:; in a dilute stream of hydrogen.

Bismuth trifluoride is not readily hydrolyzed even by boiling water. However, addition ofHF causes the formation of BiF2, '3HF, which is readily

hydrolyzed to bismuth oxytluoride (13520-7247, BiOF. Heating Bit'3 at 200-300°C in air results in the formation of some oxide or oxyfluoride. Between 600 and 800°C fluorine is gracluallyreplaced hy oxygen yielding phases such as TIiOO_1J1?_S' niOP, and, on prolonged heating (60 h at 670°C), ni?O_'). Th» so-called cubic phase of TIiF~ probahly contains some oxygen.

Complexes ofTIiF,) are almost unknown, hut crystallization from a hot solution of ammonium fluoride that has been saturated with freshly precipitatecl bismuth trioxide yields cryst.a]s of alT1TTlOTliuTTl lelTafl110TObisTllIlthaLe(TTT) [136()()-76-~7, NHL RiF 4. This complex is readily decorrrposec] by

water.

Bism uth Trichloride. Bismuth(III) chloride is a colorless, crystalline, deliquescent solid made up of pyramidal molecules (19). The nearest intermolecular Bi-Cl distances are 0.3216 run and 0.3450 run. The density of the solid is 4.75 g!mL and that of the liquid at 254°C is 3.851 g/mL. The vapor density corresponds to that of the monomeric species. The compound is monomeric in dilute ether solutions, but association occurs at concentrations greater than 0.1 AI. The electrical conductivity of molten BiOj is of the same order of magnitude as that found for ionic substances.

Bismuth trichloride is usually prepared by chlorination of the molten metal or by dissolving bismuth metal in aqua regia; evaporation of the solution yields the bismuth trichloride dihydrate /66172-88-1/, BiC~ .2112°, and upon distillation, it decomposes to give anhydrous bismuth trichloride. The commercial product frequently is not anhydrous.

Bismuth trichloride shows considerable tendency to form addition compounds. Reaction with ammonia yields the colorless, easily volatilized bismuth trichloride trimrrrnine [66l72-R9-2), TIiCl;, JNH;" as well as the red, thermally unstable hismuth trichloride herniarnmine [66172-90-5], 2TIiCl_') ·NH? Compounds offormula BiClj ·NO, BiCl3 2N02, and BiClj ·NOCllnay be isolated; these are stable in dry air but are decomposed by moisture. Bismuth


128

BISMUTH COMPOUNDS

Vul4

trichloride is soluble in organic solvents: solution is presumably accorrrpanied by the formation of complexes of the Lype:

A number of complex bismuth halides are well-known, eg, disodium bismuth pentachloride 166184-10-9), N~BiC15; sodium dibismuth heptachloride [66184-09-6j, NaBi,0); and trisodium bismuth hexachloride i66114-82-7j, NajBiCl,. TI,e acid, hydrogen dibismurh heptachloride trihydrate [66124-39-9], HnilJ7 -3H20, is a crystalline suhsranr-s-, stable at room tf'mpf'rahuf', that may he isolated hy cooling a solution of BiC13 in concentrated hvdrochloric acid to O°C.

, Bismuth Trihromidc. Bismuthfl.l l) bromide is a hygroscopic, golden-yellow, crystalline solid made up of pyramidal molecules. X-ray analysis

has shown that the three bromines are 0.263 .L 0.002 nm from the bismuth and the Br-Bi-Br angles are 100 ± 4':. More recent nqr experiments indicate that the bromines are not equivalent (20). The solid has a density of 5.72 g/mL and that of the liquid is 4.572 g/mL at 27I.SoC.

BisIllUUI tribrcmide Illay be prepared by dissolving B~03 in excess concentrated hydrobromic acid. The slurry formed is allowed to dry in air, then gently heated in a stream of nihogen to rernove water, and finally distilled in a stream of dry .nitrojzen. Bismuth uibrornide is soluble in aqueous solutions of KCl, HCl, I<J:h, and Kl but is decomposed by water to form bismuth oxybromide L7787-57-7], 1:)i01:)r. It is soluble in acetone and ether, and practically insoluble in alcohol. It fOIIIlS complexes with NH3 and dissolves in hvdrohrornic acid from which dihydr:ogen bismuth pentab toruide tetrahydra le [66214-38-8j, H2BiBrs -4H20, may be crystallized at -IO'·C.

Llisrnurb Triiodidc. BisIllllLh(III) iodide is a greenish black crystalline powder. TIle iodines are in a hexagonal dose-packed array with each bismuth having six nearest-neighbor iodines at 0.12nm (21). This suggests that the lone pair on bismuth is stereochemk-ally inactive and that the compound is largely ionic in character.

Bismuth triiodide may be prepared by heating stoichiometric quantities of the elements in a sealed tube. It undergoes considerable decomposition at 500°C and is almost completely decomposed at 700°C. However, it may be sublimed without decomposition at 3.3 kPa (25 mm Hg). Bismuth triiodide is essentially insoluble in cold water and is decomposed by hot water. It is soluble in liquid ammonia forming a red triarrrmine complex, absolute alcohol (1.5 g/100 g), benzene, toluene, and xylene. It dissolves in hydroiodic acid solutions from which hydrogen tetraiodobismuthate(III) [66214-37-7], HBiI4 -4H10, may be crystallized, and it dissolves in potassium iodide solutions to yield the red compound, potassium tetraiodobismuthate(1II) [39775-75-2], KBiI4. Compounds of the type tripotassium bismuth hexaiodide [66214-36-6], KJ1:)il6, are also known.

Bismuth Pentutluoride. Bismuth/V) fluoride consists oflong white needles that have been shown to have the same structure as the body-centered, tetragonal co-polymorph of uranium hexafluoride. The density of the solid is 5.4 g/mL at 25°C. The solid consists of infinite chains of trans-bridged BiF('j polyhedra; dimcrs and trimcrs arc present in the vapor phase (22). Bismuth pcntafluoridc may be prepared by the fluorination of BiF:'J or

metallic bismuth at 600°C_ For purification, it may be sepa:rated from l:hF3 by repeated sublimation at I20°C_ At higher temperatures it decomposes to yield BiF') and fluorine.

Bisrnurh penrafluorirle is an active flllOrinating agent. It reacts explosively with water to form ozone, oxygen difluoride, and a voluminous chocolate-brown precipitate, possibly a hydrated bismuth(V) oxyfluoride. A similar brown precipitate is observed when the white solid compound bismuth oxvtrifluoride [66172-91-6], BiOFv is hydrolyzed. Upon standing, the chocolate-brown 'precipitate slowly undergoes reduction to yield a white bisIIluth(III)

compound. At room temperature BiF~ reacts vigorously with iodine or sulfur; above 50°C it converts paraffin oil to fluorocarbons; at lS0°C it fluorinates uranium tetrafluoride to uranium pentafluoride; and at lS0°C it converts Br2 to bromine trifluoride, BrF:, and bromine pentafluoride, BrFs, and chlorine to chlorine fluoride, CIF. It apparently does not react with dry oxygen.

Treatment of BiF, with BrF~, results in the formation of fluorobromoniumhcxafluorobismulliatc(V) [36608-81-8j, [BrF ,l [BiF,J, which may be isolated as white hygroscopic crystals upon removal of excess BrFj under vacuum. TIlls compound is relatively stable but at reduced pressures undergoes decomposition to BrFJ and BiF~. .Adducrs are formed between BiF ~ and the fluorides of lithium, sodium, potassium, or silver by heating equimolar quantities of the respective compounds to 8S-1S0°C_ The resulting hexafluorobismuthate(V) compounds are more stable to reduction than l::ht's. The x-ray diffraction pattern of potassium hexafluorobismuthatefV) /26914-71-6/, KBiFe is similar to that of potassium hexatluoroantimonatefv) /16893-92-8/, KSbFs. Silver hexafluorobismuthatefV) !66184-08-5j, AgBiF" may also be formed by warming elemental silver and [BrF2l [BiF,l dissolved in BrF,. TIlls compound is hygroscopic, soluble in rIF, and reacts with water to form a chocolate-brown precipitate and probably some ozone.

llismuth Oxide Halides. Hydrolysis of a bismuth trihalide yields the corresponding bisIlluth(III) oxide halide (oxyhalide). BisIllUUI oxvlluoride [13520-72-4], BiOF, and bismuth oxyio dide [7787-63-_~7, BiOI, IIlay also he formed hy heating the corresponding bismuth uihalide in ali. \Xihen either: bismuth oxychloride or: bismuth oxybromide [7787-57-7]_, BiOBr, is heated above 700°C, complex bismuth oxyhalides of composition Bi;40~-IX-O are formed. Bismuth oxychloride {7787-59-9], BiOCI, is a white, lustrous, crystalline powder (density, 7.72 g/mL) that is practically insoluble in water, alcohol, acids, and bases. Hot concentrated alkali solutions convert it to bismuth trioxide. It is used in fmgemail polishes, lipsticks, and face powders to give a nacreous effect. A study (23) in which rats were fed 1,2, or S~/~~' BiOCI [or two years showed no carcinogenic or toxic effects. Bismuth oxyhrorrride, a white, amorphous powder, and bismuth oxyiodide, a bric-k-re-d, amorphous powder having a density of 7.92 g/Illl, are essentially insoluble in water, alcohol, acids, and bases and have been used in the manufar-mre of dry-cell cathodes.

Bismuth Oxides and Bismurhates. The only oxide of bismuth that has been definitely isolated in a pure state is bismuth trioxide. An acidic oxide that approximates the composition Bi:z0~ certainly exists. However, there is considerable question as to the exact nature of this material and the species involved. A number of other oxides have been reported, eg, bismuth oxide (1:1) /1332-64-5/, bismuth oxide (1:2), bismuth oxide (2:4) ;'12()48-50-9l, bismuth oxide (3:5), and bismuth oxide (4:9), but the evidence for their existence as chemical entities is meager at best.

IJistnuth Trioxide. RisHllllh(ITT) oxide [1304-76-3] has a corrrplicale«] polymorphisru, At times so me or the reporte-d phases deviate from B~O~, hy having too Iinle or too much oxygen; at least in one instance, because of the ready contamination ofBi_:,O~, melts with silicon, the reported phase

probably has the composition of bismuth oxide silicate [66256-73-3], S~Bi1404(i. The cornrnorr oxide, a-Bi:z0:" is a pale-yellow, monoclinic solid,


129

BISMUTH COMPOUNDS

Vul4

density = 9.32 ± 0.02 g/mL, which is stable up to 710°C Half of the hismuth atoms are five-coordinate, and half are s.ix-coordinate. 111(" lone-pail electrons on bismuth presumably occupy the sixth position for the five-coordinate bismuth and are responsible for the distortion of the o}..--ygen about the six-coordinate bismuth (24).

Bismuth trioxide may be prepared by the following methods: (1) the oxidation of bismuth metal by oxygen at temperatures between 750 and sauoe; (2) the thermal decomposition of compounds such as the basic carbonate, the carbonate, or the nitrate (700-S00°C); (3) precipitation of hydrated bismuth trioxide upon addition of an alkali metal hydroxide to a solution of a bismuth salt and removal of the water hy ignition. The gelatinous precipitate initially formed becomes crystalline on standing; it has been represented by the formula Bi(OH)j and called bismuth hydroxide [1036143 -OJ. However, no definite compound has been isolated.

BisIllUUI trioxide is 'practically insoluble in water; it is definitely a basic oxide and hence dissolves in acids to form salts. Acidic properties are just barely detectable, eg, its solubility slightly increases with increasing base concentration, presumably because of the formation of bismuth ate (III) ions, such as Bi(OHj"-;" and related species.

Bismuth trioxide forms numerous, complex, mixed oxides of varying composition when fused with CaO, SrO, BaO, and PbO. If high purity bismuth, lead, and copper oxides and strontium and calcium carbonates are mixed together with metal ratios BiPb.Sn.Ca.Cu = l.g : 0./1 : 2 : 2 : :1 01 1.95:0.6:2:2:3 and calcined at 800-835°C, the resulting materials have the nominal composition Bi1.9Fbc.,Sr2Ca,Cu30x and BL."Fbo.,Sr2Ca2Cu30x and become superconducting at about 110 K (25).

Higher Oxides of Bismuth and Related Compounds, Oxidation of either a fused mixture of sodium oxide and bismuth trioxide or a suspension of bismuth trioxide in 40-S0~/o sodium hydroxide solution yields a product in which much of the bismuth is apparently in the I 5 oxidation state. Air or oxygen are suitable oxidizing agenLs [or the molten rrrixture; so diurn hypochlorite, chlorine, l.rrornine, or so dunn persulfate IIlay be used [or the aqueous suspension. TIle reactions are favored by excess alkali, and Lhough IIIOre Ulan 90% of the bismuth is oxidized to the pentacovalent stale, the product is contaminated with considerable excess alkali. Extraction with methanol at O°C removes the excess alkali and yields pure sodium metabismuthatefV) tt 2232-994), N aBiO:. Addition of nitric or perchloric acid produces a material ranging in composition from Bi20,_ to Bi20:.' which slowly loses oxygen. TIlls material and sodium tnetahisrnut.hatefV} are very good oxidizing agenLs. TIle sodium bisrnuthate of corrrmerce varies in color from yellow 10 brown [0 blac-k. II has ahour. Lwo molecules of water pel" bismuth atom and is insoluble in wafer. It. is capahle of oxi<lizing TTHlTIganese(TT) compounds in nitric acid solution to permanganate, a reaction commonly used as a qualitative test for manganese. )J aBiO:;, oxidizes Fe:;'+ in basic medium

to FeO:Z-;4.

Sulfides and Related Compounds.

Bismuth Trisulfide. Bismuth/Ill) sulfide 1/345-07-9j, bismuth sesquisulfide, Bi,S3' is a dark-brown to grayish black crystalline solid, mp 850°C and density of 6.78 g/mL. It occurs naturally as the mineral bismuth glance and is isostructural with stibnitc, Sb2Sy It may be prepared by heating sulfur and bismuth or by the addition of a soluble sulfide to an aqueous solution of bismuth (III). It is almost insoluble in water or alkaline solutions but dissolves in concentrated nitric acid or hot concentrated hydrochloric acid. Concentrated alkali metal sulfide solutions or melts dissolve B~S:;, to yield crystalline compounds such as potassium thiobismuthatetIlf) tt 2506-13-7), KBiS2. These compounds are rapidly oxidized in air; similar compounds of silver, coppeL_, and lead occur naturally. Fusion ofB~S3 with a bismuth halide yields air-stable compounds, bismuth chlorosulfide [19264-19-8], BiCIS, bismuth bromo sulfide [14794-86-6J, HillrS, and bismuth iodosulfide [15060-32-9J, Bil.S. Other mixed halide sulfide compounds have been reported: bismuth bromide sulfide (19:3:27) {?1185-13-8], BiE;S27Bry has been shown to consist of (Bi_c_ScJoc; chains in which bismuth atoms in neighboring chains arc

linked by bromines (26). Bismuth disulfide; 12323-18-1 /, BiS" can be prepared at 5000 MFa at 1250°C. TI,e compound is a soh, gray, needlelike, crystalline solid.

Bismuth trisulfide has been used as a high temperature lubricant and has been of interest for its photo- and thermoelectric properties.

Related Compounds. Bismuth triselenide [1206R-69-(~7, ni)SeV and bismuth tritelluride [I 304--82-1], R~ Te_v are known, and in addition to the stoichiometric compounds, preparations can be made containing excess Bi, Sc, or Tc. Compounds arc also known in which some of the Tc in Bi.z Tc , is replaced by S or Se and some of the Se in Bi,Se, by S, eg, dibismuth ditellurium selenide ; 12010-72-9/, Bi,Te2Se and dibismurh ditellurium sulfide [1304-78-_~7_, Bi_:, Te2S. ~AJl of these materials are of interest for their semiconducting properties (see SEbn-:-::oNr:::Jl_~'-=T:-::JR"~).

Hisrnuth Salts, Bismuth trioxide dissolves in concentrated solutions of strong oxyacids to yield bismuth salts. Tn more dilute solutions of strong acids en in solutions of weak acids, the oxide reacts to f01111 bismuthyl or basic salts. The normal salts are velY susceptible to hydrolysis.

Bismuth Triperchlorate Pentahydrate. Bismuda(III) perchlorate pcntahydrarc [66 1 72-92-7J, Bi(CIO"),, 'SHeO, is prepared by dissolving Bi,0j in 70 ~<2 IICIO.1' Anhydrous bismuth triperchlorate 11405945-1}, Bi(OO,)3' may be prepared by heating bismuthyl perchlorate monohydrate [66172-_93-8], BiOOO L ·~O, between 80 and 100°C. ALLeIIlpLs to dissolve bismuth metal in concentrated perchloric acid have resulted in explosions. Treatment of bismuth or Bi20: with dilute solutions of perchloric acid yields hydrates of bismuthyl perchlorate.

Bismuth Trinitrate Pentahydrate. Bismuda(III) nitrate pcnrahydratc [10035-06-0}, Bi(NO,)~, '5H,O, is obtained by dissolving bismuth metal, _b~03' or: (HiO)2CO: in nitric acid. Attempts to remove the water of hydration yield monoclinic crystals of bismuthyl nitrate hemihydrate [10361-64-3J, BiONO" '1!2H,O (27). Addition of bismuth trinitrate pentalrydrare to alkali yields a product termed bismuth subnitrate which is widely used in pharmaceuticals. This material approximates the composition 6J:)~03 ·SN20:. ·9H20.

HisnJuth Trisultatc. TIismuth(TTT) sulfate [77f57-6R-O], ni?(SOJ~, is a colorless, very hygroscopic compound that decomposes above 405°C to yield bismuthyl salts and B~0J" The compound hydrolyzes slowly in cold water and rapidly in hot water to the yellow bismuthyl sulfate [12010-64-9_], (BiO)2S0'1. TIle normal sulfate is isomorphous with the sulfates of yttrium, lanthanum, and praseodymium.

Numerous other bismuth and bismuthyl salts are known, eg, bismuth triacetate /22306-37-2/, Bi(C)I30)j; bismuth phosphate /10049-01-1/, BiP04; bismuth trithiocyanate j43384-63-0j, Bi(CNS)3; bismuthyl nitrite hemihydrate j66172-94-9j, Bi0(N0;ol '1/2II20; bismuthyl carbonate hemihvdrate 15798-45-8j, (BiO)2C03 '1!2II20; etc. Bismuth is present in the anion in the oxalate complex sodium dioxalatobismuthatefIlf) 1 19033-91-lj, NaBi(C20,)2' the nirriro complex Na3J)i(J\"02)6) trisodium hexanitrobismnthnrefl Il) [1 f5515-R6-1], and the yellow, water-soluble thiosulfate complex trisodium trithiosulfatobismuthate/Hl) 166256-75-5 j, N a3Bi(S203)3'

Organobismuth Compounds

In a manner similar to phosphorus, arsenic, and antimony, the bismuth atom can be either tri- or pentacovalent. However, organo bismuth compounds are less stable thermally than the corresponding phosphorus, arsenic, or antimony compounds, and there are fewer types of organobismuth compounds. For example, with R4MX, R3-\12':" R,MX" and RMX4, where M is a Group 15 (VA) element and X is a halogen, ouly the first two types have been prepared where _\1 - Hi, but all four types are known where 1\;1 - P, As, or Sb.

'Lhe chemistry of organobismuth compounds has been described in several publications (28-31). 'Lhe use of organobismuth compounds, as well as organoantiIlIOny ones, in orgatllC synthesis has been exhaustively reviewed (32).

Primary and Secondary Bismurhmes. Only one primary and one secondary bismuthine are known, namely methylbismuthine, CH:Bill2, and dimethvlbismuthine. (CII,)2BiII (7). They are prepared by the lithium aluminum hydride reduction of methvldichlorobismuthice j 105309-90-8j, CH3Bi02, and dimerhjichlorobismurhine, respectively, in a nitrogen atmosphere at - I [)O' C. On being warmed to _·1[)n Co, methylbismurhine disproportionates to trimethylbismuthine (593-91-97, (CH')3Hi, and bismuthine. Dimethylbismuthine undergoes a similar dispropcrrionation at -15 C. Both methyl- and dirnerhvlhismuthine are stable, colorless liquids at -60°C, but at room tempemhue they decompose to trhnerhvlhisrnurhine, bismuth,


130

BISMUTH COMPOUNDS

Vul4

and hydrogen. An atteIIlpt to prepare phenylbismuthine and diphenylbismuthine [1438143-2], CpHIIBi, hy reduction of phenyldibrornobisrnuthine [39110-02-6J, C,H"BiBr2, and diphcnylbromobismuthinc [39248-62-9J, C1,HwBiBr, respectively, with hthium aluminum hydride or sodium borohydridc at low temperatures yielded only black polymeric substances of empirical formula CsIIsBi (33). It has been claimed (34) that dimethylbismuthine and diphenylhisrnutlrine can be used as cocatalysts [or the polvrnerization of ethylene (qv)_, propylene (qv)_, and 1,3-butadiene. TIle source of these bismuthiues, however, was not. meru.ioned.

Tertiary Bismuthines. A large number: of rrialkyl- and rriarylbismuthincs arc known (29). Thcy arc usually prepared by the interaction of a reactive organometallic compound and a bismuth trihalidc, a halobismuthinc, or a dihalobismuthinc. The G%ouard reagent (sec G1UG1\li"_R1J1U}':,_(_;LN~'::;) is the type of organometallic compound most widely employed in these syntheses (35-37). Organolithium (38-40), organoaluminum (41), organocadmium (42),

O1:ganOIllercury (43)_, organosodillIll organozinc (45_,46)_, and organosilver (47) cornpound s have also been used. Triphenvlljisrnuthine [603-33-8],

C13H1SBi, has been obtained in a yield by the addition of phenyltrifluorosilane and ammoniurn Iluoride to a solution of bismu th hydroxide in

hydrofluoric acid (48). The interaction of organomercury compounds and metallic bismuth has also been employed for the preparation of tertiary bismuthincs (49).

A number of tertiary bismuthines have been prepared by the interaction of a sodium diaryl- or dialkyibismuthide and an alkyl or aryl halide (SO):

This method is of particular value for the preparation of nnsvrnmerricnl tertiary bisrnuthines.

T riarylbismuthines have been synthesized by means of the N esmeyanov reaction that employs an arenediazonium salt such as the tetrafluoroborate, ;.J bisrruuh r rih alide, awl a n~dllciTlg ag(-,Tl[ (1"1). TIIP decornpositiou of iodoniurn salts in the P1"PSPTlCP of bisrruuh trichloride awl metallic bismuth also le-ads to the formation of triarylbisrnuthines. Ar3Bi (52):

Experiments with unsymmetrical iodonium salts indicate that the bismuth atom is preferentially a:rylated by the more electron-attracting aryl group.

There have been several reporLs of the formation of tertiary bisrnuthines by the action of free radicals on metallic bismuth. One method of generating the radicals involves cleavage of ethane or hexafluoroethane in a radio frequency glow discharge apparatus; the radicals thus formed are allowed [0 oxidize the metal af. -196°C (.13). Trimethvlhismnthine awllris(lritlllonmIPlhyl)hisTllIllhiTlP [5863-80-9], C?RiF0, have h(-,PTI ohrainecl by [his p roc-edure.

Other rnethccls of preparing tertiary bisrnuthines have been used only to a limited extent. These methods include the electrolysis of organOIlleLallic compounds at a sacrificial bismuth anode (54), the reaction between a sodinm+hisrnuth or potassium-bismuth alloy and an all..1~ or aryl halide (55), the thermal elimination of sulfur dioxide from tris(arenesultinato )bismuthines (56), and the interaction of ketene and a tris(dialk-ylamino)bismuthine (57).

Trialkylhisrnutlrines are colorless or: pale yellow liquids or solids, and most of them are spontaneously Ilarnrnable in au. Except [or trimethylbismuthice, these compounds cannot be distilled at ordinary pressures without decomposition (58). In general, trialkylbismuthines are not affected by water or aqueous bases but are readily hydrolyzed by Illany inorganic and organic acids. Hydrogen sulfide, Iller:captans, and selenol.s appear to be particularly effective in cleaving the carbon+bismuth bond (59,60). Trialkylbisrnuthines genenilly react with chlorine and bromine at low LeIllperaLur:es Lo form dialkylhalobismuthines (45,46):

The reaction of tris(trifluoromethyl)bismuthine with chlorine, bromine, or iodine, however, has been found to yield the corresponding bismuth trihalide and rrifluoromcthyl halide (61):

T riarylbismuthincs arc solids, which usually have sharp melting points. 1\;10st of these compounds arc unaffected by oxygen or water at ordinary temperature and are, in general, much less reactive than their trialkyl counterparts. 'Triphcnplbismurhinc can be readily distilled, bp 242°C at 1. 9 kPa without decomposition, and it has been obtained so pure that it has been used in measurements of the atomic weight ofbismuth (62). Most triarylbismuthines readily undergo oxidative addition with bromine or chlorine to yield the corresponding tria:rylbismuth dihalides:

Triphenylbismuth difluoride (202348-5J, C1,H,"BiF" has been obtained in a similar manner (63).

~AJl three carbon-bismuth bonds of tribenzylbismuthine /99715-52-3j, C21II21B~ (64) and triphenylbismuthine (65) can be cleaved by alkali metals.

Under some conditions, however, tertiary bismuthines react with sodium or potassium to yield secondary bismuthides. TIl.US a number of sodium dialkylbismuthides have been obtained by the interaction of a trialkylbismuthine and sodium in liquid ammonia (66-69):

where R - CII3, CiI:;, n-C:II7' iso-C}I7' or fl-C,jIIs. Triphenolbismurhine reacts with potassium in tetrahvdrofuran (DIP) in a similar manner (70):

Treatment of l-phenyl-2,5-dimethylbismole /88635-81-8/, CLJI13Bi, with sodium in liquid ammonia results ill. cleavage of the phenyl-bismuth bond and formation of l-sodio-2,5-climethylbismole j88644-524j, C,II,BiNa, (71):

J:\"

CH3 Bi CH3 + 2 Na

I

CeH5

J:\"

CH3 Bi CH3 + CsH5Na

I

Na

The secondary bismuthides discussed herein are useful for preparing several types of organobismuth compounds, eg, tertiary bismuthines and dibisrnuthines.

Although trialkyl- and triarylbismurhines are much weaker donors than the corresponding phosphorus, arsenic, and antimony compounds, they have nevertheless been employed to a considerable extent as ligands in transition metal complexes. The metals coordinated to the bismuth in these complexes include chromium ('12-77), cobalt (7R,79), iridium (80), iron (77,81,82), manganese (81,84), molvbdenum (72,75-77,85-89), nickel (7.1,79,90,91), niobium (92), rhodium (93,94), silver (95-97), tungsten (72,75-77,87,89), uranium (98), and vanadium (99). TIle coordination compounds fanned from tertiary bismuthines are less stable than those formed from tertiary phosphines, arsines, or stibines.

Tertiary his.rnuthines appear to have a number of uses in synthetic organic chemistry (12), eg, they promote the formation of'i,l,2-h"isuhstihlteil cyclcpropanes by the interaction of electron-deficient olefins and dialkyl dibromornalcnates (100). They have also been employed for the preparation of thin films (qv) of supen-onrlnctiug bismuth strontium calcium copper oxide (101), as cor-atalysts for the polymerization of alkynes (102), as inhibitors of the flammability of epoxy resins (103), and for a number of other industrial purposes.

f Ialobisrnurhines, Dihalobism uthines, and Related Compounds, Chloro-, dichloro-, bromo-, and dib rornobismuthines are best prepared hy the reaction of a tertiary bisrnuthine and bismuth trichloride or tribromide (7,43,45,46,104-107):


131

BISMUTH COMPOUNDS

Vul4

Iodo- and diiodobismuthines are easily obtained by the reaction of the corresponding chloro-, dichloro-, bromo-, or dibromobisrnuthine with SOdilUTI or potassium iodide (107-110).

Several halo- and dihalobisrnuthines have been prepared by the radial alkylation 01: arylation of bisruuth trichloride or tribromide with an organocadmium (111), organolead (112,113), organotin (114,115), or organozinc reagent (45). The reaction of a Gtignard reagent with a bismuth rrihalide usually leads to the formation of a tertiary bismuthinc. In a few cases, however" it has been possible to isolate a halo- or dihalobismuthinc from this type of reaction (116). Apparently, no fluoro- or ditluorobismuthine has ever been isolated. The formation ofbis(trifluoIOlnedl.}i)f:luorobisllluthill_e j124252-79-5j, C1J:ht<'I' by the interaction of tris(trifluoromethyl)bismuthine and iodine pentafluoride has, however, been sugg;ested by 19_b' nmr spectroscopy (117).

Halo- and dihnlobismurhines He crystalline solids, most of which have 1llelting points above 100°C. They are, in general, yery reactive corrrpounris and are decomposed by moisture, alcohols, and ammonia (118). Dialkjdhalobismuthines are especially sensitive substances. They are spontaneously inllarnrnable in ali and Illay decompose even when water and oxygen are excluded. TIle diaryl compounds are rn.ore stable, hut Lhey should also he handled with caution. Some of them are powerful sternutators (119).

A number of compounds of the types RBiY,;, or ~BiY_, where Y is an anionic group other than halogen, have been prepared by the reaction of a

dihalo- or halobisrnuthine with a Iithiurn, sodiurn, potassium, ammoniurn, silver, or lead alkoxicle (120,121)_, amide (122,123)_, azide (124,125), carboxylate (121,126), cyanide (125,127), dithiocarbamate (128,129), mercaptide (130,131), nitrate (108), phenoxide (120), selenocyanate (125), silanolate (132), thiocyanate (125,127), or xanthate (133). Dialkyl- and diarylhalobismuthines can also be readily converted to secondary bismuthides by treatment with an alkali metal (50,105,134):

Dibismuthines. Only about a dozen tetraalkyl- and tetraaryldibismuthines are known (135). These compounds can be obtained by the reaction of a sodium dialkyl- or diarylbismuthide and a 1,2-dihaloethane (66-69):

2 R2BiNa I XCH2CH2X 'R2BiBiR2 I CH2~CH2 I 2 NaX

where X = CI or 131. Several dibismurhines have also been obtained by the addition of the stoichiometric amount of sodium to a solution of a halobismuthine in liquid ammonia (105,136-139):

where X - CI or 1. TIle best method for the synthesis of tetraphenyidibismuthice l7065-21-6j, C2iI2J3i, involves the reduction of diphenvliodobismuthine [95f125·92-6J, C12HlOTIiT, using his(cydopentaclien}~)cohalt(TT) (l27743-6J, C1oHlOCo, (140):

Dibismuthines tend to be thermally unstable. Thus tetramethyldibismuthine j82783-70-8j, CJI12B~, decomposes at 25°C to yield trimethylbismuthice and metallic bismuth (66):

Tetraethyldibismuthine [81956-27-6], C}-~JBi_:,_, undergoes a similar reaction at 40°C (67). At O°C this dibismurhinc as well as tctra-f-tolyldibismnrhinc [114245-28-2J, C"H2SBi" (105) decompose to form dark polymeric solids:

where R = C2HS or 4-CH3C6Hc Tetraphenvldihismutlrine and 2,2'_,S_,5'-tetraluethylhihisIllOle [88635-82-9], C12H::_6Bi_:" (71), however, are stable to 100°C. At lOO°C the tetraphenyl compound decomposes to triphenylbismuthine and metallic bismuth (6&).

Dibisrnuthines are very sensitive to oxidation. TIllis tetramethvldilrisrnuthine fumes in air, and tetraphenyldiliisrnuthine in toluene solution rapidly absorbs oxygen. Under controlled conditions, dibismuthines react with chalcogens resulting in cleavage of the bisrnuth-Lismnth bond and insertion of a chalcogen atom (105,138,140-142):

where Y = 0, S, Se, or Te. Dibismuthines undergo a variety of other interesting reactions and have attracted considerable attention because a number of these substances are thermochromic (135).

Bismin and Its Derivatives. Bismin 1289-52-1j (bismabenzene}, C5II5B~ the bismuth analogue of pyridine, has never been isolated, but it can be formed in solution by the dehydrohalogenation of 1-chloro-l,4-dihydrobismin [19553-69-0j, CsH,5BiCl, using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) ar Iow temperatures (114,143,144):

o +DBU - 0 +DBU·HCI I

CI

-l-Methylbismin [82995-62-8], C6H./Bi, and 4-ten-butylbismin [82995-64-0), COlHuBi, have been obtained in solution by similar reactions. The presence of bismin and its 4-alkyl derivatives in these solutions has been demonstrated both by spectroscopy and via chemical trapping with 1,1,l,4,4,4-hexafiuoro-2-hutyne to yield Diels-Alder ad ducts. TIle potential arornaticity of the bisrnin ring systeIll has aroused considerable interest and has been investigated with a variety of spectral methods. '1 here seems to be little doubt that bismin does possess aromatic character.

Diarylbismuthinie Acids and Their Esters. Although organobismuth(V) compounds containing three, four, or five Bi-C bonds are well-known, no compounds containing two such bonds had been prepared until a number of methyl diarylbismuthinates (diarylmethoxybismuth oxides) were reported in 1988 (145).

Ar2Bi(O) OCH] + ArH

- 4-CH,C6H4S02NH2 + NaC]

where Ar - C.)Is, 4-CII3C6II" 3,4-(CII3)2C6II3' I-naphthyl, or 4-CII3-1-naphd,yl. TI,e yields varied from 10% (Ar - 4-CII3C,II.) to 80%

(Ar = 1 - naphthyl and 4-CH3-1-naphthyl). \Nl1en Arwas 2-CH3C5H.'1 the product was di-Zcrolvlhisrnuthinic acid [124066-74-6} rather than the ester. The reaction was unsucc-essful when Ar was 4-C1C6H4' 3-Cr;,C"H4, or 2-thiellyl. The 1llethyl esters underwent ester exchange when recrvstallizerl from ethyl en isopropyl alcohols. 1\fethyl diphenylbismurhinate [124066-62-2}, C13H::_)~i02' was readily hydrolyzed in water to rliphenylhismuthinic acid [124066-70-2]


132

BISMUTH COMPOUNDS

Vul4

Because organobisIlluth(V) cornpound s have found considerable use as oxidizing agents_, the oxidizing abilitv of methyl di-l-naphthylbisIIluthinate [124066-66-6], C:z1H::_,/Bi01, was investigated. Benzoin yields benzil, naphthalene, and metallic bismuth; hydrazobenzene yields azcbenzene, and 1,1,2,2-tetra-phenylethanediol yields benzophenone. 1,2-Diphenyl-l,2-ethanedione dihydrazone gives diphenylacetylene in SOS/~:, yield. Cyclohexane-l,2-diol and I-phenylethane-l,2-diol, however" were unaffected.

Trialkyl- and Triarylbismuth Dihalidcs and Related Compounds. After the tertiary bismuthines, the triarylbismuth dihalides constitute the most important class of organobismuth compounds and are by far the largest class of compounds containing pentacovalent bismuth. However, only two trialkylbismnth dihalides have been prepared (146). These are cs-tripropenylbismuth dibromide [66173-00-0J, C,H15BiBr2, and trans-tripropenylbismudl. dibromide 166212-224j, C91I15BiBr2, prepared by oxidative brorninaticn of the corresponding bismuthines at -,j5 C. With most trialkylbismuthines studied to date, cleavage of one carbon+bismuth bond occurs 011 halogenation:

By contrast, triarylbismuthincs arc readily chlorinated or brominatcd to the corresponding dichloridcs or dibromidcs using chlorine or bromine. Other chlorinating agents include sulfur dichloride, sulfur mono chloride, thionyl chloride, and iodine trichloride. T riarylbismuth di±luorides have been prepared from the dichlorides by metathesis with potassium fluoride or by direct fluorination of triaryibismuthines with fluorine diluted with argon. K 0 triaryibismuth diiodides are known. However, the two compounds triphenylbismuth iodide azide! I06112-77-0j, (C6IIS)jBi(I)N 3' and triphenylbismuth iodide isocyanate [I06112-78-IJ, (C,)Isl3Bi(I)NCO, have been prepared from triphenjlbismuthine and iodine azide or iodine isocyanate, respectively (147). The triarylhistuurh dihalides are stable c-rystalline solids with high melting points. X-ray studies, conductivities, and other physical rneasuremerrts snggest that the bismuth atom in these compounds has trigonal-bipyramidal geOlnetry.

In addition to the halides ArjB~, a large number of compounds of the type ArjBiY2' where Y is NO:", Ny CK, ocn, CH:,C02, CF::,CO:l' 1/2 CO::' 1/2 SO 4-' 0jSR, etc, can be prepared by metathesis from the dihalidcs and a silver, sodium, or potassium salt of the desired anion. The disulfonatcs (C,Hsl3lll(03SR)2 have been prepared from the carbonate and the appropriate sulfonic acid (14S). A number of mixed carbonates 1\r,1\r'lliCU3, as well as mixe-d dichlorides Ar/h'RiCl» have been 'prepared. (149). Tripheuvlbisrruuh ciicCll'hoxylalPs have been obtained hy se-veral different. methods indwiing 11](-, following (150):

The majority of the COIllPOLIUds of the type _A...I3Bi"{:2 an:' stable crystalline solids, soluble in organic solvents. TIH::'y give norrual molecular weights in solvents such as benzene.

'l'riphenylbismuth oxide ;7173-99-17, CSH1SlliU, has been prepared from triphenylbismuth dicyanide (41083-16-37, C2J-i1jlliN" and mercuric oxide (151), and from triphenylbismuth dichloride and moist silver oxide (152). The ir and Raman spectra of this compound suggest that it is polymeric and has Br-Or-Bi bonds (153). 'l'riphenylbismuth dihydroxide, C13Hl'lliU" and triarylbismuth hydroxide halides, eg, triphenylbismuth hydroxide chloride ;'66214-57-17, C13H16BiCIO, have been reported in the earlier chemical literature. There is, however, no modem research on these types of compounds, and they Inay or Inay not exist.

In recent years o:rganobisIlluth(V) compounds have found increasing use as reagents in organic synthesis. TIlUS they have been used [or the oxidation of primary and secondary alcohols to the corresponding aldehydes (qv) and ketones (qv), for the oxidative cleavage of vicinal glycols (qv), and for the 0-, C-, and N-arylation of a wide variety of organic compounds. Because most of these reactions occur under relatively:mild conditions, organobismuthfv) reagents have proved to be of particular value when the substrates are sensitive natural products. Several review articles on this subject have been published (32,154-156), and a patent on the oxidation of steroidal, terpene, and sugar alcohols to the corresponding aldehydes (qv) and ketones (qv) has been issued (lS7) (see SUG_IIJ'_£:-::O::-::CJLS). Although other types of organohisIlluth(V) compounds, Ar4BiY and ArsBi, have been used, the triaryl compounds Ar:"BiY 2 arc the reagents of choice because of their ease of preparation and chemical stability.

In addition to usc in organic synthesis, triarylbismuth dihalides and related compounds have found limited industrial usc. A patent has been issued for the use of such compounds as antifungal agents on plastics or fibrous material (158). Compounds of the type (C6Hs),Di(02CR)2' eg, triphenjdbismuth dimethacrylate 133 71-98-0j, C'6II2sBiO., and triphenylbismuth bis (4-vinylbenzoate) i 218148-8 j, C3sII'9BiO l' are claimed to be effective agents against StaplJ)'ioCOCClI,'atireIlS infections (159). Triphenylbismuth dichloride 1594-30-9j, CjSILsBiCl" is active against bean rust (160). Triardbismuth clihalides have been used as catalysts for the carbonation of epoxides to form cyclic carbonates (161).

Quaternary Bismuth Compounds. Although earlier attempts had been made to prepare quaternary bismuth compounds, it was not until 1952 that rctraphcnvlbismuth bromide [66173-02-2], C24H20BiBr, was obtained from pcnraphcnylbismuth [J049-07-(~7, C3Ji2SBi, and one molar equivalent of bromine at - 71Y C (162):

In a similar manner tetraphenylbismuth chloride 142967-53-3./, C24II2cBiO, (162) and tetraphenylbismuthoniurn tetrafluoroborate l36682-02-7j, C2JI20BBiF 4' (163) are obtained from pentaphenyibismuth and hydrogen chloride or hydrogen tetrafluorobo.rate, respectively. \Xihen triphenylboron is used, the tetraphenylborate is obtained (162):

A number of other tetruarvllrisnmth compounds Al)~iY, where Y is a group, such as NO 00 ;4,0C":N ;, N ;.» etc, have been prepared from the

chloride hy metathesis. Two tetraalkylhisrnuth cornpound s have been reportedly prepared hy rneans of the following synthesis (164):

When triphenylbismuth dichloride, in acetone, is treated with silver perchlorate, in absolute ethanol, tetraphenylbismuthonium perchlorate [43047-28-5], C2.c.H2oBiCI04' is formed (165). If, however, the same reaction is carried out only in acetone, the following reaction occurs (166):

The corresponding tetrafluorohorate is obtained when sflverterraflnoroborate is used.

Quaternary bismuth compounds are generally unstable. When the anionic ligand is chloride or bromide, the compounds decompose spontaneously on slawling; azides awl selenocyarrafes decompose rnore rapidly. TIle pen-hl Of"(J Ips, retrafluoroborares, awl he-xafluorophophares, howe-ve-r, are cOTlsi<leT"ahly more stable but eventually decompose. 'Lhe 'vibrational spectra of the latter compounds show the presence of the free ion and are consistent with a tetrahedral BiC4 skeleton for the cation. The acetonyltriphenyl compounds, [(C,Hs),BiCH2COCH3lY, where Y is ClO-;4 or BF-;4' also appear to be true bismuthonium salts.

Quaternary bismuth compounds have not found extensive use in industry or in organic synthesis. In manifold studies of organobismuthfv) compounds as oxidizing and arylating agents, such quaternary bismuth compounds as (C6H)4Bi02CCH::p (C6H~)4BiOJSC6H4CHJ~4, and


133

BISMUTH COMPOUNDS

Vul4

(CI~H_J4BiO;CCF) have been errrployed (32). There seern.s to be no marked advantage of the quaLerruu:y compounds over the rrrore stable and tHOH:' easily prepared compounds of the type Ar;TIiY?"

Bismuthonium Ylides. Prior to 1988 the only bismuthcnium piides known were (1) and (2).

(1)

(2)

(3)

Structure (1) is an uusrnble blue solid which cannot be obtained in a purf' starr- (167); structure (2) [IOS071-90-7_7, however, is stable (168). Strnctnre (2) was obtained from triphenylbismuth carbonate and dimedone. More recently a number of bismuthonium ylides, eg, (3) [1/9016-81-8] (169), have been prepared and their reactions studied.

Reactions of these compounds with phenylisothiocyanate and a number of aromatic and aliphatic aldehydes have been investigated (169,170). Only where R is 4-CH_,OC,H4 or C6HcCH~CH arc the normal Wittig products obtained:

Using a number of other aldehydes, more complicated products result. Structure (2) was also found to :react with alkjnes in the presence of copper(I) chloride to give furans:

+ RC==CH

HC=CR

O~6

CuCI

-

H3C CH3

where R is C,Hc,- 4-CH_,C6Hc, 4-CIC,Hc,- hcxyl, and C,Hc,COCH,. An excellent gencral method for the preparation of bismuthonium vlidcs from diazo compounds has been devised in which bis(hexafluoroacetylacetonato)copper(II) is employed as a catalyst (171). Two relatively stable ylides prepared by this procedure are (4) [117968-30-6} and (5) [117968-31-7]. TIle latter compound did not react with 2,4-dirritIObenzaldehyde.

o ~Bi(C6H5h o

(5)

Quiriquenary Ris1TIUth Compounds, No pentaalkvllrisnmth compounds have been reported, but a number of pentaaryihisrnurh compounds are known. Pentaphenclbisnmth [J049-fJ7-R}, C:')(H?_"iRi, was first prepared by means of the reaction (162):

It can also be prepared by the reaction of phenyllithium with tetraphenylbismuth chloride or the ~'\I-triphenylbismuth derivative of -l-tolnenesulfonamide (172):

Pcntaphcnylbismuth is a violet-colored, crystalline compound that decomposes spontaneously after standing for several days in a dry nitrogen atmosphere. \Vidl. a variety of agents, eg, hydrohalic acids, halogens, and triphenylboron, one phenyl group is cleaved to form quaternary bismuth compounds.

The deep violet color of pcntaphcnvlbismnth and certain other pcntaarylbismuth compounds has been the subject of considerable speculation. It has been shown by x-ray diffraction (173) that the bismuth atom in pcntaphcnylbismuth is square+pyramidal. Well-formed crystals arc dichromic, appearing violet when viewed in one plane but colorless in another plane. The nature of the chromophore has been suggested to be a charge-transfer transition by excitation of the four long equatorial bonds:


134

BISMUTH COMPOUNDS

Vul4

In supporL of this suggeslion, it has been shown that stt:ong electron-withd rawinjz subs Lituents 011 the aryl groups, which would make the charge-traIlsfer transition more difficult, result in less highly colored compounds. Thus bis(pentafluorophenyi)triphen,1bismuth /111210-36-7/, C3filSBiFl0' is an orange-colored solid. A number of pentaarylbismuth compounds that vary in color from violet, bis(4-fluorophenyl)tri-4-tolylbisllludl. tt 24652-38-6), C,.,H",BiF2, to yellow, bis(pentafluorophenyl)tri-4-tolylbismuth (118798-77-9], C33H31BiF", have been prepared (174). Structures that could be determined

by x-ray diffraction all exhibit square-pyramidal geometry.

Pentaphenylbismuth has been studied as a reagent in organic synthesis where it can act either as an oxidizing or an a:rylating agent. TIlUS it can be used for the oxidation of primary or secondary alcohols to aldehydes or ketones, respectively. Unlike compounds of the type A.r:3BiY2 or A.r:4BiY that require the presence of a strong base for the oxidation of alcohols, pentaphenylbismuth oxidizes alcohols under neutral conditions. Thus benzyl alcohol is oxidized to benzaldehyde in 45Sio yield by pentaphenylbismuth; 3~-cholestanol gives the corresponding ketone in 70% yield. Penraphenylbismuth can also act as an arylating agenL. 2-N apluhol reacts to give Lphenyl-Zcnaphthol in 61%1 yield (C-arylation)_, hut phenol gives diphenyl ether in 42~/o yield (O-arylation). Often both oxidation and phenylation occur. Thus estradiol gives a mixture of 2,4-diphenylestrone, 4-pheny:Lestrone, and 2,4-diphenyicstradiol. When 2-phen,1cthanol is treated with pcntaphcnjdbismuth, triphcnrlacctaldchydc is produced in 69% yield.

Bismuth Compounds Used in Medicine

Therapeutic properties were first attributed to bismuth during the seventeenth century, and bismuth compounds were tried for the treatment of both syphilis and gonorrhea before the end of the eighteenth centll1Y (I IS). During the 1 920s, it was shown that bismuth compounds were comparable in efficacy to the best antisvphilic drugs then available (175). During the next quarter of a century, bismuth compounds became widely used as adjuncts to the arsenical therapy of syphilis (176). However, antibiotics (qv), especially penicillin, have made hoth arsenic and bismuth compounds completely obsolete for the treatment of this disease (177,178).

Bismuth compounds were once employed for the treatment of amoebic dysentery, certain skin diseases, and several spirochetal diseases besides syphilis, but these substances are now seldom considered the drugs of choice. Various insoluble preparations of bismuth, especially the subcarbonate, subnitrarc, subgallate, subcitratc, and sub salicylate, arc still employed for the treatment of ulcers and other gastrointestinal disorders, even though use for these purposes is often supported largely by tradition. With a few possible exceptions, it is now difficult to justify the presence of bismuth compounds in a modern therapeutic armamentarium. A review of the biological activity of organobismuth compounds has been published (179).

Bismuth sub salicylate 114882-18-9./, Pepto-Bismol, is a basic salt ofvaryicg composition, corresponding approximately to o-IIOC6II'IC02(BiO). Like a number of other insoluble bismuth preparations, it is not currently approved in the United States for the treatment of peptic ulcer disease hut is under active investigation for this purpose (180). It does appear to be effective for the relief of mild diarrhea and for the prevention of travelers I diarrhea (181). The ready availability of this drug, however, lnay lead to its overuse and result in toxic effects caused by both the salicylate and bismuth components. It has been suggested that bismuth sub salicylate is somewhat effective in the symptomatic treatment of isosporiasis, a disease caused by the intracellular parasite TWIi)Onl belli (I ~2).

Bismuth subcarbonate /3892-1047 (basic bismuth carbonate) is a white or pale yellow powder that is prepared by interaction of bismuth nitrate and a water-soluble carbonate. 111e exact composition of this (hug depends on the conditions of precipitation; it corresponds approximately to the formula (BiO)2C03. It has been widely used as an antacid (183).

'L'ripotassium dicitratobismuthate ;'57644-54-97 (bismuth subcirrate). De-Nol is a buffered aqueous suspension of a poorly defined, water-insoluble bismuth compound. It is said to very effective for the treatment of gastric and duodenal ulcers (180,184). There have not yet been any reports of bismuth encephalopathy following the use of this drug.

Bismuth subnitratc [1304-854] (basic bismuth nitrate) can be prepared by the partial hydrolysis of the normal nitrate with boiling water. It has been used as an antacid and in combination with iodoform as a wound dressing (183). Taken internally, the subnitrate may cause fatal nitrite poisoning because of the reduction of the nitrate ion by intestinal bacteria.

Bismuth suhgallate [12552-60-2] (basic bismuth gallate), Dermurol, is a hright yellow powder that can he prepared by the interaction of bismuth nitrate and gallic acid in an acetic acid medium. It has been employed as a dusting powder in some skin disorders and as an ingredient of suppositories for the trearrneut of hemo rrhoids (181, I S5). It has been taken orally for many years hI' colostomy patients in order to control fecal odors, hut the dIug may cause serious neurological problems (186).

BIBLIOGRil.PHY

"Bismuth Compounds" in ECT 1st cd., Vol. 2, pp. 533-538, by R. Pasternack, Charles Pfizer & Co., Inc.; "Bismuth Preparations" in ECT 1st cd., Vol. 2, pp. 538-540, by G. o. Doak, C.S. Public Health Service Laboratory of Experimental Therapeutics.Tohns Hopkins School of Hygiene: "Bisnuuh Conrpouruls" in ECT2nd ed., Vol. 3, pp. 535-549, hy G. O. Doak, L. D. Freedman, and G. G. Long, North Carolina Suue University; 'IBisIllllLh Compounds" in Hel· 3rd ed., Vol. 3, pp. 921-937, by G. G. Long, 1.. D. Freedman, and G. O. Doak,).f orth Carolina State University.

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2. T. M. Hopes. in S. Williams, ed., Official Methods of Analy,-is of the Association ofOiJieial Analytical Cbosists, 14th ed., Association of Official Analytical Chemists, Athngton, Va., 1984, p. 672.

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21. J. Trotter and T. Zobel, Z Kristallo,~n7,tJh. 123,67 (1966).

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24. G. Malmros, Ada Chan. 5mm/ 24, 384 (1970).

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136

BISMUTH COMPOUNDS

96. s. .Ahrland, T. Berg, and P. Trinderup, Acta Chem. Stand So~AA31_, 775 (1977).

97. F. Hultiin and 1. Persson, InotX. Cbi». Aela 128, 43 (1987).

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112. A E. Goddard,J~. Ashley, and RB. Evans,J Cbem. Soc. 121, 978 (1922).

113. L. Maicr, Tetmbedron Lelt. (6),1 (1959).

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115. :\f. 1. Anishchenko, E. M. Panov, O. P. Svutkina, and K.. A. Kocheshkov, Zh. Obsheh. Khim. 49, 1185 (1979).

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127. F. Challenger and J. F. Wilkinson,). Cbem. J·oc. 121, 91 (1922).

128. E. J. Kupchik and C T. Thciscn,]. Organomet. Cbe». 11,627 (1968).

129. \{. Wieher and A. Dasel, 7. A nOll. AIIg. Oem. 44R, 89 (1979).

130. '11. Wiebcr, 1. Fctzcr-Krcmling, D. Wirth, and H. G. Rr.dling, Z. Allorg. AIIg. Gem. 520, 59 (1985).

111. T. KlaPlltke,J 0llanomet. Cbem .. "\,"\1, 299 (1987).

132. H. Schmidb aur and 1vI. Bergfeld, Z. Anol);. AI{~. Oem. 363, 84 (1968).

133. '11. Wieher, H. G. JU,dling, and Ch. Burschka, Z. Anorg. Allg. Chon. 470, 171 (1980).

134. D. D. Davis and C. E. Gray, Organomel. Chem. &'>. S ect. A 6, 283 (1970).

135. A. J. Ashe, III,Adv. 0llartomet. Chem. 30, 77 (1990).

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139. '11. Wieber and 1. Sauer, Z. Naturforse!>., Tei/ B 39B, 887 (1984).

140. F. Calderazzo and co-workers, lnorg. Cbe»: 27,3730 (1988).

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142. \{. Wieher and T. Saner, 7. Naturfnmh., Teilll.WTI, 1668 (1984).

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150. V. A. Dodonov, A. V. Gushchin, and M. B. Ezhova, Zh. ObJhh. Khim. 58,2170 (1988).

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Vul4

137

BISMUTH COMPOUNDS

Vul4

174. A. Schmuck and K Seppelt, Chem. Bet: 122, 803 (1989).

175. C. Levaditi, L11:cet204, 639 (1923).

176. J. E. Moore, The Nlodem Treaune»: of Syphilis, 2nd ed., Charles C. Thomas, Springfield, m., 1941, pp. 134-153.

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181. L. L. Brunton, in Ref. 180, p. 925.

182. Dntg J.,lJaluatirJns, 6th erl., American Medic-al Association Department of Drugs, \V. B. Saunders Company, Philadelphia, Pa.,1986, p. 1.168.

183. J. E. F. Reynolds, cd., Alarlim/a!e. The ExllYJ PhatJJJacopoeia, 29th cd., The Pharmaceutical Press, London, 1989, p. 1548.

184. Ref. 183,pp. 1111,1112.

185. Ref. 182,1" 973.

186. F. P.Morgan and].]. Billings,Nlerl.JA7Isl. (2),662 (1974).

G. Gilbert Long Leon D. Freedman G. O. Doak

North Carolina State University


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