Synthesis and structures of plutonyl nitrate complexes: is plutonium heptavalent in PuO3(NO3)2(-) ?

Gas-phase plutonium nitrate anion complexes were produced by electrospray ionization (ESI) of a plutonium nitrate solution. The ESI mass spectrum included species with all four of the common oxidation states of plutonium: Pu(III), Pu(IV), Pu(V), and Pu(VI). Plutonium nitrate complexes were isolated in a quadrupole ion trap and subjected to collision-induced dissociation (CID). CID of complexes of the general formula PuOx(NO3)y(-) resulted in the elimination of NO2 to produce PuOx+1(NO3)y-1(-), which in most cases corresponds to an increase in the oxidation state of plutonium. Plutonyl species, Pu(V)O2(NO3)2(-) and Pu(VI)O2(NO3)3(-), were produced from Pu(III)(NO3)4(-) and Pu(IV)(NO3)5(-), respectively, by the elimination of two NO2 molecules. CID of Pu(VI)O2(NO3)3(-) resulted in NO2 elimination to yield PuO3(NO3)2(-), in which the oxidation state of plutonium could be VII, a known oxidation state in condensed phase but not yet in the gas phase. Density functional theory confirmed the nature of Pu(V)O2(NO3)2(-) and Pu(VI)O2(NO3)3(-) as plutonyl(V/VI) cores coordinated by bidentate equatorial nitrate ligands. The computed structure of PuO3(NO3)2(-) is essentially a plutonyl(VI) core, Pu(VI)O2(2+), coordinated in the equatorial plane by two nitrate ligands and one radical oxygen atom. The computations indicate that in the ground spin-orbit free state of PuO3(NO3)2(-), the unpaired electron of the oxygen atom is antiferromagnetically coupled to the spin-triplet state of the plutonyl core. The results indicate that Pu(VII) is not a readily accessible oxidation state in the gas phase, despite that it is stable in solution and solids, but rather that a Pu(VI)-O· bonding configuration is favored, in which an oxygen radical is involved.