Experimental and Quantum Mechanical Characterization of an Oxygen-Bridged Plutonium(IV) Dimer

We report the synthesis and characterization of K₄ {[PuCl₂ (NO₃ )₃ ]₂ (μ₂ -O)}⋅H₂ O, which contains the first known μ₂ -oxo bridge between two Pu^IV metal centers. Adding to its uniqueness is the Pu-(μ₂ -O) bond length of 2.04 Å, which is the shortest of other analogous compounds. The Pu-(μ₂ -O)-Pu bridge is characterized by the mixing of s-, d-, and p-orbitals from Pu with the p-orbitals of O; the 5f-orbitals do not participate in bonding. Natural bond orbital analysis indicates that Pu and O interact through one 3c-2e σ_Pu-O-Pu and two 3c-2e π_Pu-O-Pu bonding orbitals and that the electron density is highly polarized on the μ₂ -O. Bond topology properties analysis indicates that the Pu-(μ₂ -O) bond shares both ionic and covalent character. Quantum mechanical calculations also show that the dimer has multiconfigurational ground states, where the nonet, septet, quintet, triplet, and singlet are close in energy. This work demonstrates the interplay between experimental and computational efforts that is required to understand the chemical bonding of Pu compounds.