The compound [Co(CO)3(μ3-Bi)]4 has been obtained by prolonged pyrolysis of [BiCo(CO)43] in refluxing tetrahydrofuran. This species, isomorphous with the analogous [Co(CO)3(μ3-Sb)]4, crystallizes in the tetragonal space group I4d1/amd (No. 141) with a 14.731(3), c 10.574(3) Å and Z = 4. The structure was refined by full-matrix least-squares, on the basis of 447 significant unique reflections, to a final R value of 0.032. The compound has a cubane-like structure, with four tetrahedrally disposed Co(CO)3 units triply bridged by four Bi atoms. The BiCo bonds have a mean value of 2.745 Å. Each cobalt atom exhibits a highly distorted octahedral coordination, with BiCoBi and CCoC angles of mean value 75.48 and 101.1°. The Co...Co contacts are definitely non-bonding (mean 4.291 Å). the non bonding Bi...Bi interactions (mean 3.360 Å) are particularly short. The mean values of the CoC and CO bond lengths are 1.78 and 1.19 Å, respectively. © 1989.
Ciani, G., Moret, M., Fumagalli, A., Martinengo, S. (1989). BI-CO HETERONUCLEAR CARBONYL-COMPOUNDS - SYNTHESIS AND CRYSTAL-STRUCTURE OF THE CUBANE-LIKE SPECIES [CO(CO)3(MU-3-BI)]4. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 362(3), 291-296 [10.1016/0022-328X(89)87250-X].
BI-CO HETERONUCLEAR CARBONYL-COMPOUNDS - SYNTHESIS AND CRYSTAL-STRUCTURE OF THE CUBANE-LIKE SPECIES [CO(CO)3(MU-3-BI)]4
MORET, MASSIMO;
1989
Abstract
The compound [Co(CO)3(μ3-Bi)]4 has been obtained by prolonged pyrolysis of [BiCo(CO)43] in refluxing tetrahydrofuran. This species, isomorphous with the analogous [Co(CO)3(μ3-Sb)]4, crystallizes in the tetragonal space group I4d1/amd (No. 141) with a 14.731(3), c 10.574(3) Å and Z = 4. The structure was refined by full-matrix least-squares, on the basis of 447 significant unique reflections, to a final R value of 0.032. The compound has a cubane-like structure, with four tetrahedrally disposed Co(CO)3 units triply bridged by four Bi atoms. The BiCo bonds have a mean value of 2.745 Å. Each cobalt atom exhibits a highly distorted octahedral coordination, with BiCoBi and CCoC angles of mean value 75.48 and 101.1°. The Co...Co contacts are definitely non-bonding (mean 4.291 Å). the non bonding Bi...Bi interactions (mean 3.360 Å) are particularly short. The mean values of the CoC and CO bond lengths are 1.78 and 1.19 Å, respectively. © 1989.
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