Molecular Assemblies Based on Cp*BiX₂ Units (X = Cl, Br, I): An Experimental and Computational Study

Two in one: the bismuth bromido clusters in [Bi6Cp*6Br9][Bi7Br24]

“…However, to the best of our knowledge, {Bi 6 X 9 } moieties (X = halogen) as reported here are rare. Similar arrangements are restricted to recently reported examples such as [Bi 6 Cp * 5 Cl 12 ] + (Monakhov et al, 2011). In 1a, the bromine atoms Br1 and Br3 bridge three bismuth atoms while the interstitial atom Br2 is located in the center of the Bi 6 octahedron with symmetric coordination to the six bismuth atoms with a Bi1-Br2 distance Scheme 1 Proposed reaction scheme for the formation of compound 1.…”

“…Reaction of A with unreacted BiBr 3 (Eq. 3) gave the title compound 1, in analogy to the reaction between BiX 3 (X = Cl, Br) and Cp * Li as described recently for similar Cp * -substituted bismuth halides (Monakhov et al, 2011). Monakhov et al observed the formation of a mixture of BiCp * Br 2 (A) and [{Bi 5 Cp * 5 Br 9 }{BiBr 4 }] 2 upon reaction of LiCp * with BiBr 3 .…”

“…The structure of B reveals in the solid state a chain of Cp * Bi units bridged by tetraiodoaluminate ions. Ionic bismuth halido clusters similar to 1 were reported recently (Monakhov et al, 2011). The reaction between BiX 3 (X = Cl, Br) and LiCp * gave compounds such as [Bi 6 Cp * Br 9 ] [Bi 7 Br 24 ] (1) represents another example within the family of these novel organobismuth halido clusters.…”

“…In 1a, the bromine atoms Br1 and Br3 bridge three bismuth atoms while the interstitial atom Br2 is located in the center of the Bi 6 octahedron with symmetric coordination to the six bismuth atoms with a Bi1-Br2 distance Scheme 1 Proposed reaction scheme for the formation of compound 1. (Üffing et al, 1999) and [Bi 6 Cp * 5 Cl 12 ] + (2.250 Å) (Monakhov et al, 2011). The [Bi 6 Cp * 6 Br 9 ] 3+ cluster might be described to be built from six Cp * Bi-based units as presented in Figure 3C.…”

“…For example, BiCp * Br 2 (A) was reported by Jutzi and Schwartzen in 1989, prepared from metallic bismuth and 5-bromopentamethyl-1,3-cyclopentadiene. Recently, the single crystal X-ray structure analysis of A was reported (Monakhov et al, 2011). Another example is [Al(η 5 -Cp * ) 2 {Bi(η 5 -Cp * )}(μ-AlI 4 ) (AlI 4 ) 2 ] * 2C 7 H 8 (B), which was obtained upon reaction of (AlCp * ) 4 with BiI 3 in toluene (Üffing et al, 1999).…”