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Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores
Matthew A Stuber1, Anna Y Kornienko1, Thomas J Emge1
1Department of Chemistry and Chemical Biology, Rutgers, the State University of New Jersey , 610 Taylor Road, Piscataway, New Jersey 08854-8087, United States.
Abstract:
Tetrametallic thorium compounds with a Th4E4 core (E = S, Se) having a distorted cubane structure can be prepared by ligand-based reductions of elemental E with thorium chalcogenolates, prepared by in situ oxidation of Th metal with a 3:1 mixture of PhEEPh and F5C6EEC6F5. Four compounds, (py)8Th4S4(μ2-SPh)4(SC6F5)4, (py)8Th4S4(μ2-SPh)4(SeC6F5)4, (py)8Th4Se4(μ2-SePh)4(SeC6F5)4, and (py)8Th4Se4(μ2-SePh)4(SC6F5)4, were isolated and characterized by NMR spectroscopy and X-ray diffraction. These compounds clearly demonstrate the chemical impact of ring fluorination, with the less-nucleophilic EC6F5 ligands occupying the terminal binding sites and the EPh ligands bridging two metal centers. For this series of compounds, crystal packing and intermolecular π···π and H-bonding interactions result in a consistent motif and crystallization in a body-centered tetragonal unit cell. Solution-state 77Se NMR spectroscopy reveals that the solid-state structures are maintained in pyridine.
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