Synthesis, structural and spectroscopic characterisation of three di-μ-fluoro-bis[dioxouranyl] complexes |
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Authors: | Gordon H John Iain May David Collison Madeleine Helliwell |
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Institution: | aCentre of Radiochemistry Research, Department of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK bDepartment of Chemistry, The University of Manchester, Oxford Road, Manchester M13 9PL, UK |
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Abstract: | Three novel uranyl complexes with organic phosphine oxide ligands and bridging fluorides have been synthesised and structurally characterised. In UO2(μ-F)(TPPO)3 2]BF4]2 · nC6H14, 1, and UO2(-μF)(TBPO)3 2]BF4]2 2, (where TPPO and TBPO are triphenylphosphine oxide and tri-n-butylphosphine oxide, respectively) two UO2 2+ moieties are bridged by two fluorides with three additional terminal PO donor ligands coordinated to each uranium centre. The dicationic complexes are both charge balanced by two uncoordinated tetrafluoroborate anions. In the related structure, UO2(μ-F)(F)(DPPMO2)]2 · 2MeOH (3), terminal fluoride is also coordinated to both uranyl centres (where DPPMO2 = bis(diphenylphosphine oxide)methane). All three complexes were prepared during attempted syntheses of complexes with tetrafluoroborate directly coordinated to uranium. It is clear from these results that the fluorophilicity of UO2 2+ causes the abstraction of fluoride from BF4]−, with the weakly coordinating anion only present as a counter cation in 1 and 2, and absent completely in 3. |
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Keywords: | Uranyl Fluoride Phosphine oxide ligands Structural study Spectroscopic characterisation |
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