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.

The major difference arises from the rate of the oxidative addition to Pd(0) into a C-Bi bond or C-O one, yielding cycles A and B, respectively (see image).

Among the first representatives of the organometallic bismuth chemistry are a series of iron cyclopentadienyl compounds synthesized by Cullen et al.

Compounds derived from various transition metal carbonyl complexes are organometallic representatives with somewhat unusual cyclic structure and electronics.

[7] 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.

Upon heating, the hexametallic tribismuth-trirhenium heteronuclear complex undergoes isomerization to cis- and trans-clusters containing the bicyclo [3.3.0] core (see scheme below).

The core of such compounds is represented in the form of dibismuthene or dibismithyne unit, in which the Bi atoms contain the inert 6s lone pair and through π-bond-donation are able to coordinate to carbonyl moieties of transition metals .

[2] 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].

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) [ 2 ]
Mono-, bi-, and trimetallated bismuth-iron cyclopentadienyl complexes [ 2 ]
Syntheses of bismuth-manganese organometallic complexes employs bismuth trichloride salt as the bismuth-containing starting material [ 2 ] [ 3 ] [ 4 ] [ 5 ]
Summary of metal-bismuth carbonyl complexes syntheses [ 2 ] [ 6 ] [ 7 ] [ 8 ]
Isomerization of bismuth-rhenium cluster carbonyl compounds [ 8 ]
Cyclobismuthane reaction with metal carbonyl complexes [ 9 ] [ 10 ]
Examples of dibismuthene complexes [ 2 ] [ 11 ] [ 12 ]
Synthesis of [{Cp(μ 2 -CO)Fe} 3 (μ 3 -Bi)] [ 2 ]
Spiro-like and cubane-like bismuth clusters [ 2 ]
Synthesis of bismuth "paddlewheel" complexes [ 14 ] [ 15 ]