The coordination chemistry of cationic main group clusters: syntheses and structures of [Fe3(Se2)2(CO)10] and [Fe4(Se2)3(CO)12] |
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Authors: | Greg W Drake George L Schimek Joseph W Kolis |
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Institution: | Department of Chemistry, Clemson University, Clemson, SC 29634 1905, USA |
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Abstract: | The reactions of the polysulfur and selenium cationic clusters S82+ and Se82+ with various iron carbonyls were investigated. Several new chalcogen containing iron carbonyl cluster cations were isolated, depending on the nature of the counteranion. In the presence of SbF6? as a counterion, the cluster Fe3(E2)2(CO)10] SbF6]2·SO2 (E = S, Se) could be isolated from the reaction of E82+ and excess iron carbonyl. The cluster is a picnic-basket shaped molecule of two iron centers linked by two Se2 groups, with the whole fragment capped by an Fe(CO)4 group. Crystallographic data for C10O12Fe3Se4Sb2F12S (I): space group monoclinic P21/c, A = 11.810(9), b = 24.023(6), c = 10.853(7) Å, β = 107.15(5)°, V = 2942(3) Å3, Z = 4, R = 0.0426, Rw = 0.0503. When Sb2F11? is present as the counterion, or Se4Sb2F11]2 is used as the cluster cation source, a different cluster can be isolated, which has the formula Fe4(Se2)3(CO)12] SbF6]2·3SO2. The dication contains two Fe2Se2 fragments bridged by an Se2 group. Crystallographic data for C12O18Fe4Se6Sb2F12S3 (III): space group triclinic
, b = 18.400(9), C = 10.253(4) Å, = 93.10(4), β = 103.74(3), γ = 93.98(3)°, V = 1995(1) Å3, Z = 2, R = 0.0328, Rw = 0.0325. The CO stretches in the IR spectrum all show a large shift to higher wavenumbers, suggesting almost no τ backbonding from the metals. This also correlates with the observed bond distances. All the compounds are extremely sensitive to air and water, and readily lose SO2 when removed from the solvent. Thus all the crystals were handled at ?100°C. The clusters seem to be either insoluble or unstable in all solvents investigated. |
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Keywords: | Crystal structures Iron complexes Selenium complexes Carbonyl complexes Cluster complexes |
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