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Bismuth organometallic chemistry

The stabilization of bismuth's +3 oxidation state due to the inert pair effect yields a plethora of organometallic bismuth-transition metal compounds and clusters with interesting electronics and 3D structures.[1]

Structure

Summary of metal-bismuth carbonyl complexes syntheses[2][3][4][5]

As is typical for bismuth compounds, the 6s electron pair is mainly inert. Organometallic Bi(III) compounds are Lewis acids, similar to group 13 element organometallic chemistry.[2]

Also similar to boron compounds, bismuth forms a wide variety of metal clusters.[2] Most synthetic routes use bismuth trichloride as the bismuth metal source.[6]

Below, compounds are sorted roughly by increasing electron delocalization.

Classical σ bonding

In the simplest case, Bi forms a simple σ bond to another metal. For example, cyclopentadienyldicarbonyliron (Fp) is isolobally a pseudohalide:[7][8]

Mono-, bi-, and trimetallated bismuth-iron cyclopentadienyl complexes
Mono-, bi-, and trimetallated bismuth-iron cyclopentadienyl complexes

With cobalt tetracarbonyl instead of Fp, there exist similar compounds,[7] which are Lewis acids. The formal adduct with cobaltocenium tetracarbonylcobalt is the tetrahedral, paramagnetic [Cp2Co][Bi{Co(CO)4}4] complex.[3]

An analogous manganese compound forms a delocalized Mn-Bi-Mn bond:[2][6]

Syntheses of bismuth-manganese organometallic complexes employs bismuth trichloride salt as the bismuth-containing starting material
Syntheses of bismuth-manganese organometallic complexes employs bismuth trichloride salt as the bismuth-containing starting material

Polybismuth ligands

Other clusters contain a formal dibismuthene or dibismithyne unit, coordinated through the Dewar–Chatt–Duncanson interaction.[2] For example, oligo-trimethylsilylbismuth(I) reacts with pentacarbonyltungsten tetrahydrofuran to give a cluster with a Bi-Bi bond length corresponding to a single bond:[9][10]

Cyclobismuthane reaction with metal carbonyl complexes[9][10]
Cyclobismuthane reaction with metal carbonyl complexes[9][10]

Another example comes in the form of a zirconocene unit, side-coordinated to a dibismuth mesitylene moiety (pictured below).[11]

In 2009, Pearl et al. described the synthesis and isomerization of heterometallic complexes containing bismuth and rhenium. The precursors used in synthesis were an alkene-coordinated carbonyl rhenium complex and BiPh3.[5] The reaction yields two types of heteronuclear bismuth-rhenium complexes and a homodinuclear rhenium one as a side product. Upon heating, the hexametallic tribismuth-trirhenium heteronuclear complex undergoes isomerization to cis- and trans-clusters containing the bicyclo [3.3.0] core. Under subsequent irradiation both stereoisomers convert to a common spiro [4.3] cluster compound:[5]

Isomerization of bismuth-rhenium cluster carbonyl compounds[5]
Isomerization of bismuth-rhenium cluster carbonyl compounds[5]

Clusters like closo-[Bi3Cr2(CO)6]3- and [Bi3Mo2(CO)6]3- have been reported to stabilize the ozone-like structure of [Bi3]3-.[4] The [Bi3]3- species, isostructural and isoelectronic with ozone, can be analyzed independently as a moiety bound to the metal carbonyl complexes. The reported Bi-Bi distance falls in between the single and double bond region and is elongated compared to Bi=Bi bond in the [Bi4]2- cluster, the later displaying a bond order of 1.25.[4] This experimental observation is being rationalized by some amount of π-donation to the metal carbonyl center and simultaneously π* back-bonding to the bismuth cluster from the metallocene complex.[4]

PSEPT-type clusters

Bismuth atoms may appear at a wide variety of positions in a polyhedral skeleton:[2][12]

Examples of dibismuthene complexes[2][12][11]
Examples of dibismuthene complexes[2][12][11]

Strained cluster complexes with monodentate as well as bridging carbon monoxide units have also been isolated, such as [{Cp(μ2-CO)Fe}3(μ3-Bi)] and [(μ3-Bi)Co3(CO)6(μ-CO)3]:[2][13]

Synthesis of [{Cp(μ2-CO)Fe}3(μ3-Bi)][2]
Synthesis of [{Cp(μ2-CO)Fe}3(μ3-Bi)][2]

Spiro-like clusters such as [{Ru2(CO)8}(μ4-Bi){(μ-H)Ru3(CO)10} and cubane-like ones as [Bi4Co*4] are representatives as well. The former displays a tetracoordinate bismuth metallic center along with a dicoordinated hydride ligand. The structure of the latter is cubic with the edges alternating bismuth and cobalt metallic centers:[2]

Spiro-like and cubane-like bismuth clusters[2]
Spiro-like and cubane-like bismuth clusters[2]

Applications

Organobismuth compounds have been proposed as non-toxic nucleophile partners in Suzuki-Miyaura-type coupling reactions. Transmetallation to organopalladium compounds occurs by two different mechanisms:[2]

Carbon-carbon bond formation catalyzed by bismuth organometallic compounds can proceed through two different mechanisms depending on the rate of the oxidative addition to Pd(0)
Carbon-carbon bond formation catalyzed by bismuth organometallic compounds can proceed through two different mechanisms depending on the rate of the oxidative addition to Pd(0)

In cycle A, Pd(0) oxidative addition occurs faster with the nucleophile's C-Bi bond; in cycle B, it occurs faster with the electrophile's C-O one.

"Paddlewheel" complexes

Inspired from the dirhodium tetraacetate bimetallic salt, synthetic chemists decided to explore the synthesis of paddlewheel mixed heteronuclear bismuth-rhodium salts. The synthesis involves treatment of the [Rh2(O2CR)4] salt with the dibismuth tetrafluoroacetate [Bi2(O2CCF3)4] equivalent.[14][15] Depending on the nature and sterics of the R ligand, the resulting mixed salt has either two tBu R-substituents resulting in the cis mixed salt or a single Me R-substituent provenient from the dirhodium precursor:

Synthesis of bismuth "paddlewheel" complexes[14][15]
Synthesis of bismuth "paddlewheel" complexes[14][15]

The mixed salts display increased air and moisture sensitivity compared to the parental dimetallic salts and show Lewis acidity at the rhodium center.[2]

See also

References

  1. ^ Braunschweig, Holger; Cogswell, Paul; Schwab, Katrin (January 2011). "Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond". Coordination Chemistry Reviews. 255 (1–2): 101–117. doi:10.1016/j.ccr.2010.07.002.
  2. ^ a b c d e f g h i j k l m Braunschweig, Holger; Cogswell, Paul; Schwab, Katrin (2011-01-01). "Synthesis, structure and reactivity of complexes containing a transition metal–bismuth bond". Coordination Chemistry Reviews. 255 (1): 101–117. doi:10.1016/j.ccr.2010.07.002. ISSN 0010-8545.
  3. ^ a b Leigh, J. Scott; Whitmire, Kenton H. (1988). "[Cp2Co][Bi{Co(CO)4}4 ]: A Paramagnetic, Ten-Electron, Tetrahedral Complex of Bismuth". Angewandte Chemie International Edition in English. 27 (3): 396–398. doi:10.1002/anie.198803961. ISSN 0570-0833.
  4. ^ a b c d Xu, Li; Ugrinov, Angel; Sevov, Slavi C. (2001-05-01). "Stabilization of Ozone-like [Bi3]3- in the Heteroatomic closo -Clusters [Bi3Cr2(CO)6]3- and [Bi3Mo2(CO)6 ]3-". Journal of the American Chemical Society. 123 (17): 4091–4092. doi:10.1021/ja0038732. ISSN 0002-7863. PMID 11457165.
  5. ^ a b c d Adams, Richard D.; Pearl, William C. (2009-10-05). "Rhenium−Bismuth Carbonyl Cluster Compounds". Inorganic Chemistry. 48 (19): 9519–9525. doi:10.1021/ic901176x. ISSN 0020-1669. PMID 19711899.
  6. ^ a b Von Seyerl, Joachim; Huttner, Gottfried (1980-08-19). "Wismut(I)-chlorid, BiCl, als komplexligand: darstellung und struktur von [C5H5(CO)2Mn)2BiCl]2". Journal of Organometallic Chemistry. 195 (2): 207–212. doi:10.1016/S0022-328X(00)90005-6. ISSN 0022-328X.
  7. ^ a b Cullen, W. R.; Patmore, D. J.; Sams, J. R. (1973). "Synthesis of transition metal derivatives of arsenic, antimony, and bismuth with M-E sigma bonds". Inorganic Chemistry. 12 (4): 867–872. doi:10.1021/ic50122a032. ISSN 0020-1669.
  8. ^ Cullen, W. R.; Patmore, D. J.; Sams, J. R.; Newlands, M. J.; Thompson, L. K. (1971-01-01). "Cyclopentadienyldicarbonyliron derivatives of arsenic, antimony and bismuth with M–Fe σ-bonds (MAs, Sb, Bi)". Journal of the Chemical Society D: Chemical Communications (16): 952–953. doi:10.1039/C29710000952. ISSN 0577-6171.
  9. ^ a b Balázs, Lucia; Breunig, Hans Joachim; Lork, Enno (2002-07-03). "Synthesis of the Dibismuthene Complex [{μ-η2-(cis-Me3SiCH2Bi)2}{W(CO)5}2] from a Cyclobismuthane and [W(CO)5(thf)]". Angewandte Chemie International Edition. 41 (13): 2309–2312. doi:10.1002/1521-3773(20020703)41:13<2309::AID-ANIE2309>3.0.CO;2-M. ISSN 1433-7851. PMID 12203575.
  10. ^ a b Breunig, Hans Joachim (2005). "Organometallic Compounds with Homonuclear Bonds between Bismuth Atoms, 70 Years after Paneth' Report on the Violet Dimethyl Bismuth Compound". Zeitschrift für anorganische und allgemeine Chemie. 631 (4): 621–631. doi:10.1002/zaac.200400476. ISSN 0044-2313.
  11. ^ a b Wang, Yuzhong; Quillian, Brandon; Yang, Xiao-Juan; Wei, Pingrong; Chen, Zhongfang; Wannere, Chaitanya S.; Schleyer, Paul v. R.; Robinson, Gregory H. (2005). "A Metallocene-Complexed Dibismuthene: Cp2Zr(BiR)2 (Cp = C5H5; R = C6H3-2,6-Mes2)". J. Am. Chem. Soc. 127 (21): 7672–7673. doi:10.1021/ja051704h. PMID 15913345.
  12. ^ a b Martinengo, Secondo; Ciani, Gianfranco (1987-01-01). "Bismuth–cobalt heteronuclear carbonyl cluster compounds. Synthesis and X-ray characterization of the neutral [BiCo3(CO)9] and of the paramagnetic anion [Bi2Co4(CO)11]–". Journal of the Chemical Society, Chemical Communications (20): 1589–1591. doi:10.1039/C39870001589. ISSN 0022-4936.
  13. ^ Whitmire, Kenton H.; Leigh, J. Scott; Gross, Michal E. (1987-01-01). "Isolation and characterization of the 'strained' cluster complex, (μ3-Bi)Co3(CO)6(μ-CO)3; the application of thermogravimetric analysis to rational cluster reactions". Journal of the Chemical Society, Chemical Communications (12): 926–927. doi:10.1039/C39870000926. ISSN 0022-4936.
  14. ^ a b Dikarev, Evgeny V.; Li, Bo; Zhang, Haitao (2006). "Tuning the Properties at Heterobimetallic Core: Mixed-Ligand Bismuth−Rhodium Paddlewheel Carboxylates". J. Am. Chem. Soc. 128 (9): 2814–2815. doi:10.1021/ja058294h. PMID 16506756.
  15. ^ a b Dikarev, Evgeny V.; Li, Bo; Rogachev, Andrey Yu.; Zhang, Haitao; Petrukhina, Marina A. (2008-08-01). "Metal-Site-Controlled Arene Coordination in a Heterobimetallic Bi−Rh Complex with Pyrene". Organometallics. 27 (15): 3728–3735. doi:10.1021/om8001763. ISSN 0276-7333.
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