Crown ether complexes of uranyl, neptunyl, and plutonyl: hydration differentiates inclusion versus outer coordination.

The structures of actinyl-crown ether complexes are key to their extraction behavior in actinide partitioning. Only UO2(18C6)(2+) and NpO2(18C6)(+) (18C6 = 18-Crown-6) have been structurally characterized. We report a series of complexes of uranyl, neptunyl, and plutonyl with 18-Crown-6, 15-Crown-5 (15C5), and 12-Crown-4 (12C4) produced in the gas phase by electrospray ionization (ESI) of methanol solutions of AnO2(ClO4)2 (An = U, Np, or Pu) and crown ethers. The structures of 1:1 actinyl-crown ether complexes were deduced on the basis of their propensities to hydrate. Hydration of a coordinated metal ion requires that it be adequately exposed to allow further coordination by a water molecule; the result is that hydrates form for outer-coordination isomers but not for inclusion isomers. It is demonstrated that all the actinyl 18C6 complexes exhibit fully coordinated inclusion structures, while partially coordinated outer-coordination structures are formed with 12C4. Both inclusion and outer-coordination isomers were observed for actinyl-15C5 complexes, depending on whether they resulted from ESI or from collision-induced dissociation. Evidence for the formation of 1:2 complexes of actinyls with 15C5 and 12C4, which evidently exhibit bis-outer-coordination structures, is presented.