:Organobismuth chemistry

Triethylbismuth, the first known organobismuth compound, was prepared in 1850 by Löwig and Schweizer from iodoethane and a potassium–bismuth alloy. As with most trialkylbismuth compounds, BiEt₃ has an extremely pungent and unpleasant odor, and is spontaneously oxidized in air.{{Cite book |last=R. |first=King |title=Encyclopedia of Inorganic Chemistry |publisher=Wiley |year=2005 |isbn=9780470860786 |edition=2nd |volume=I: A-C |pages=345–369}} The chemistry of these complexes first began receiving significant attention when Grignard reagents and organolithium compounds became available.

File:CH3BiCl2.svg

Triorganobismuth(III) compounds are monomeric with pyramidal structures reminiscent of organophosphorus(III) chemistry. The halides however adopt hypervalent structures. This trend is illustrated by the sheet-like structure adopted by methylbismuth dichloride.{{cite journal |last1=Althaus |first1=Henrik |last2=Breunig |first2=Hans Joachim |last3=Lork |first3=Enno |title=Syntheses and Chemistry of Methylantimony and Methylbismuth Dihalides: An Extended Two-Dimensional Framework in the Crystal Structure of CH₃BiCl₂ and Molecular Units in the Structures of [CH₃ECl₂(2,2'-bipyridine)] (E = Sb, Bi) |journal=Organometallics |date=February 2001 |volume=20 |issue=3 |pages=586–589 |doi=10.1021/om000749i }}

Most aliphatic organobismuth(III) compounds oxidize easily, with the lighter members pyrophoric. Dialkylhalobismuthines cannot be stored, as they decompose under even inert atmospheres.{{Cite book |last1=Freedman |first1=Leon D. |title=The Chemistry of the Metal—Carbon Bond |last2=Doak |first2=George O. |publisher=Interscience |year=1989 |isbn=0471915564 |editor-last=Hartley |editor-first=Frank Robinson |series=(Patai's) Chemistry of Functional Groups |volume=5 |location=Chichester, UK |pages=413–436 |chapter=The use of organoantimony and organobismuth compounds in organic synthesis |doi=10.1002/9780470772263.ch9}}{{Rp|page=413}}

Diarylbismuthines are among the most powerful sneezing agents known.{{Rp|page=413}}

Organobismuth heterocycles are based on Bi(III). The cyclic compound bismole, a structural analog of pyrrole, has not been isolated, but substituted bismoles are known.{{cite book |last1=Caster |first1=Kenneth C. |chapter=Arsoles, stiboles, and bismoles |pages=857–902 |editor1-last=Katritzky |editor1-first=Alan R. |editor2-last=Rees |editor2-first=Charles Wayne |editor3-last=Scriven |editor3-first=Eric F. V. |title=Comprehensive Heterocyclic Chemistry II: Five-membered rings with one heteroatom and fused carbocyclic derivatives |date=1996 |publisher=Pergamon |isbn=978-0-08-042725-6 }} Bismabenzene has been detected in the laboratory.{{cite journal |last1=Gagnon |first1=Alexandre |last2=Dansereau |first2=Julien |last3=Le Roch |first3=Adrien |title=Organobismuth Reagents: Synthesis, Properties and Applications in Organic Synthesis |journal=Synthesis |date=2 March 2017 |volume=49 |issue=8 |pages=1707–1745 |doi=10.1055/s-0036-1589482}}

The most general and widely-used methodology for homoleptic trialkyl- and triarylbismuth complex synthesis reacts BiX₃ with organolithium or -magnesium reagents:

:BiCl₃ + 3RMgX → R₃Bi + 3MgXCl

:BiCl₃ + 3LiR → BiR₃ + 3LiCl.

Triorganobismuth compounds were first prepared instead from K₃Bi and organic halides:

:K₃Bi + 3RX → BiR₃ + 3KX.

This method is generally more difficult and produces a lower yield. However, it remained as of 2006 the only method for e.g., (Me₃Si)₃Bi synthesis.

Triaryl bismuth(III) compounds are typically air-stable crystalline solids, and the substituents will react before the carbon-bismuth bonds under appropriate conditions:{{cite journal |last1=Hébert |first1=Martin |last2=Petiot |first2=Pauline |last3=Benoit |first3=Emeline |last4=Dansereau |first4=Julien |last5=Ahmad |first5=Tabinda |last6=Le Roch |first6=Adrien |last7=Ottenwaelder |first7=Xavier |last8=Gagnon |first8=Alexandre |title=Synthesis of Highly Functionalized Triarylbismuthines by Functional Group Manipulation and Use in Palladium- and Copper-Catalyzed Arylation Reactions |journal=The Journal of Organic Chemistry |date=1 July 2016 |volume=81 |issue=13 |pages=5401–5416 |doi=10.1021/acs.joc.6b00767 |pmid=27231755}}

File:Gagnon_Synthesis_of_Functionalized_Triaryl_Bi(III)_Reagents.pngAsymmetric organobismuth compounds proceed most naturally from the (unstable) organobismuth halides RBiX₂ and R₂BiX.

In industry, triarylbismuth compounds catalyze various alkene and alkyne polymerizations.{{Rp|page=415}}

Triarylbismuth compounds have very limited use in organic synthesis.{{cite journal |last1=Finet |first1=Jean Pierre |title=Arylation reactions with organobismuth reagents |journal=Chemical Reviews |date=1 November 1989 |volume=89 |issue=7 |pages=1487–1501 |doi=10.1021/cr00097a005 }} Their bonds are weak, and easily displaced by other elements, metallic or nonmetallic.{{Rp|page=413}} Such reactions proceed more readily than for the lighter congeners. Of course, triphenylbismuth undergoes redistribution with its trihalide to give the mixed derivatives such as diphenylbismuth chloride (Ph₂BiCl).{{cite journal |last1=Barton |first1=Derek H. R. |last2=Bhatnagar |first2=Neerja Yadav |last3=Finet |first3=Jean-Pierre |last4=Motherwell |first4=William B. |date=January 1986 |title=Pentavalent organobismuth reagents. Part vi. Comparative migratory aptitudes of aryl groups in the arylation of phenols and enols by pentavalent bismuth reagents |journal=Tetrahedron |volume=42 |issue=12 |pages=3111–3122 |doi=10.1016/S0040-4020(01)87378-6}} Bbismuth(III) reagents can transfer substituents to thallium(III) compounds:{{Rp|page=414}}

Bi(CH₂=CMe)₃ + 3 TlCl₃ → (CH₂=CMe)₂TlCl + 2 BiCl₃ at −40 °C

File:N-Arylation_2.pngLikewise acylchlorides react under Pd(0) catalysis to form a variety of phenyl ketones.{{cite journal |last1=Barton |first1=Derek H.R. |last2=Ozbalik |first2=Nubar |last3=Ramesh |first3=Manian |title=The chemistry of orqanobismuth reagents: Part XIII ligand coupling induced by Pd(0) |journal=Tetrahedron |date=January 1988 |volume=44 |issue=18 |pages=5661–5668 |doi=10.1016/S0040-4020(01)81427-7 }} Although not formally arenes, tricyclopropylbismuth(III) reagents react with aryl halides and triflates under Pd(0) catalysis in a similar fashion to afford a variety of aryl and heteroaryl cyclopropanes:{{cite journal |last1=Gagnon |first1=Alexandre |last2=Duplessis |first2=Martin |last3=Alsabeh |first3=Pamela |last4=Barabé |first4=Francis |title=Palladium-Catalyzed Cross-Coupling Reaction of Tricyclopropylbismuth with Aryl Halides and Triflates |journal=The Journal of Organic Chemistry |date=1 May 2008 |volume=73 |issue=9 |pages=3604–3607 |doi=10.1021/jo702377h |pmid=18363369 }}

File:Transmetallating_Bi(III).png

The thermal stability of R₅M compounds decrease in the order As > Sb > Bi. The aryl compounds are more stable than alkyl compounds. Me₅Bi decomposes explosively at 20°C.{{fact|date=September 2021}}

The nature of the aryl ligands is important in determining whether the complex's geometry is trigonal bipyramidal or square planar and its color. In general, homoleptic compounds of the type Ar₅Bi adopt square pyramidal structures. The pentaphenyl compound is deeply colored and thermochromic, possibly because of equilibration between geometries.{{cite journal |last1=Schmuck |first1=Arno |last2=Seppelt |first2=Konrad |title=Strukturen von Pentaarylbismut-Verbindungen |journal=Chemische Berichte |date=May 1989 |volume=122 |issue=5 |pages=803–808 |doi=10.1002/cber.19891220502}}

Carboxylates rarely form chelating complexes of bismuth. Instead, organobismuth carboxylates are typically polymeric, with each oxygen on the carboxylate coordinating to a different bismuth atom.{{Cite book |title=The Chemistry of Organic Arsenic, Antimony, and Bismuth Compounds |publisher=Wiley |year=1994 |isbn=047193044X |editor-last=Patai |editor-first=Saul |editor-link=Saul Patai |series=Chemistry of Functional Groups |location=Chichester, UK |doi=10.1002/0470023473}}{{Rp|pages=330-332,344-345}} The same is not true for xanthates.{{rp|334,340}}

Bismuth halides coordinated to arenes are piano-stool complexes.{{rp|337,341-343}}

Interestingly, although very few inorganic Bi^V compounds are known, there is a wide variety of pentacoordinate organobismuth complexes.{{Rp|page=415}} Triarylorganobismuth complexes easily oxidize to bismuth(V) complexes when treated with chlorine or bromine, giving Ar₃BiX₂ (X = Cl, Br). Reactions with iodine instead displace ligands to give tricoordinate Ar_3−xBiI_x, whilst reactions with fluorine are too vigorous for control.

All-carbon organobismuth(V) complexes may then be accessed from displacement of the newly formed bismuth-halogen bond with an alkyl or aryl lithium or Grignard reagent. For example:

: Me₃Bi + SO₂Cl₂ → Me₃BiCl₂ + SO₂

: Me₃BiCl₂ + 2 MeLi → Me₅Bi + 2 LiCl

Unstable, purple Ph₅Bi was the first to be synthesized so.

Bi(V) easily forms an onium ion for example by protonation with p-toluenesulfonic acid:{{cite journal |last1=Barton |first1=Derek H. R. |last2=Charpiot |first2=Brigitte |last3=Dau |first3=Elise Tran Huu |last4=Motherwell |first4=William B. |last5=Pascard |first5=Claudine |last6=Pichon |first6=Clotilde |title=Structural Studies of Crystalline Pentacalent Organobismuth Compounds |journal=Helvetica Chimica Acta |date=14 March 1984 |volume=67 |issue=2 |pages=586–599 |doi=10.1002/hlca.19840670227 }}

: Ph₅Bi + HO₃SAr → Ph₄Bi⁺[O₃SAr⁻]

Pentaphenylbismuth forms an ate complex upon treatment with phenyl lithium:{{cite journal |last1=Wallenhauer |first1=Stephan |last2=Leopold |first2=Dieter |last3=Seppelt |first3=Konrad |title=Hexacoordinate organobismuth compounds |journal=Inorganic Chemistry |date=September 1993 |volume=32 |issue=18 |pages=3948–3951 |doi=10.1021/ic00070a029}}

: Ph₅Bi + PhLi → Li⁺[Ph₆Bi⁻]

Organobismuth(V) reagents are useful for a wide variety of organic transformations. Compared to their lighter congeners, Bi(V) compounds are strong oxidants, dehydrogenating alcohols of all kinds to the carbonyl and cleaving glycols to the aldehyde. They also engage in aryl transfers.

The compounds Ph₃Bi(OOtBu)₂, Ph₃BiCO₃ and (Ph₃BiCl)₂O have been investigated for oxime, thiol, phenol, and phosphine oxidation.Organobismuth Chemistry Hitomi Suzuki, Yoshihiro Matano Elsevier, 2001{{pn|date=September 2021}} In general, oxidation accelerates when the aryl ligands have electron-withdrawing substituents, and attacks alcohols before thiols or selenides.{{Rp|pages=416-417}} Hydrazines dehydrogenate to azo compounds and thiols to a mixture of sulfides and disulfides.{{Rp|pages=417-418}} High yields require strongly basic conditions (absent it, the carbonate is the most effective), suggesting that the active species are triarylbismuth oxides. However, pentaarylbismuth compounds will also abstract hydrogen.{{Rp|pages=416-417}}

In general, bismuth(V) compounds arylate inefficiently, transferring only one of the five ligands to the substrate{{cite journal |last1=Elliott |first1=Gregory I. |last2=Konopelski |first2=Joseph P. |date=July 2001 |title=Arylation with organolead and organobismuth reagents |journal=Tetrahedron |volume=57 |issue=27 |pages=5683–5705 |doi=10.1016/S0040-4020(01)00385-4}} and leaving behind a triarylbismuth(III) waste. Reoxidizing the Bi^III complex to Bi^V is hard, and impedes closing a catalytic cycle around this chemistry. Nevertheless, Ph₅Bi and Ph₃BiCl₂ do arylate 1,3-dicarbonyls and arenes:{{cite journal |last1=Barton |first1=D. H. R. |last2=Finet |first2=J.-P. |date=1 January 1987 |title=Bismuth(V) reagents in organic synthesis |journal=Pure and Applied Chemistry |volume=59 |issue=8 |pages=937–946 |doi=10.1351/pac198759080937 |s2cid=96332137 |doi-access=free}}

:File:PentaphenylbismuthArylation.svg

In the reaction, the bismuth(V) reagent loses an aryl group and binds to oxygen. The subsequent arylation and elimination are asynchronous and concerted:{{cite journal |last1=Barton |first1=Derek H.R. |last2=Bhatnagar |first2=Neerja Yadav |last3=Finet |first3=Jean-Pierre |last4=Motherwell |first4=William B. |title=Pentavalent organobismuth reagents. Part vi. Comparative migratory aptitudes of aryl groups in the arylation of phenols and enols by pentavalent bismuth reagents |journal=Tetrahedron |date=January 1986 |volume=42 |issue=12 |pages=3111–3122 |doi=10.1016/S0040-4020(01)87378-6 }}

File:Alpha-arylation_mechanism.png

Adjacent electron-pair donors determine regioselectivity.

In the presence of a copper salt, such reagents arylate amines and alcohols. Under ultraviolet light as well, they monoarylate glycols. Steric hindrance governs their high selectivity: secondary alcohols are arylated over tertiary ones, and axial alcohols arylated over equatorial ones.{{Rp|pages=417-431}}

{{Main|Bismuthinidene}}

Bismuthinidene are analogous to carbenes since they have the general form R-Bi, with two lone pairs of electrons on the central bismuth(I) atom. Bismuthinidenes are unstable and very reactive due to the unusual +1 oxidation state but can be used in catalysts.

• {{Annotated link|Bismuth organometallic chemistry}}

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{{Bismuthides}}

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Category:Organobismuth compounds