Organouranium chemistry

Organouranium chemistry is the science exploring the properties, structure and reactivity of organouranium compounds, which are organometallic compounds containing a carbon to uranium chemical bond. The field is of some importance to the nuclear industry and of theoretical interest in organometallic chemistry.

The development of organouranium compounds started in World War II when the Manhattan Project required volatile uranium compounds for ²³⁵U/²³⁸U isotope separation. For example, Henry Gilman attempted to synthesize compounds like tetramethyluranium and others worked on uranium metal carbonyls but none of the efforts met success due to organouranium instability. After the discovery of ferrocene in 1951, Todd Reynolds and Geoffrey Wilkinson in 1956 synthesized the uranium metallocene Cp₃UCl from sodium cyclopentadienide and uranium tetrachloride as a stable but extremely air-sensitive compound. In it the U-Cl bond is an ionic bond and the uranium bonds with the three cyclopentadienyl ligands are covalent of the type found in sandwich compounds with involvement of the uranium 5f atomic orbitals.

Ernst Otto Fischer in 1962 discovered tetracyclopentadienyluranium Cp₄U by reaction of NaCp with UCl₄ (6% yield) as a compound stable in air as a solid but not in solution. A zero molecular dipole moment and IR spectroscopy revealed that it was also a sandwich compound with uranium in a tetrahedral molecular geometry. In 1970, Fischer added Cp₃U to the list of known organouranium compounds by reduction of Cp₄U with elemental uranium.

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