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A comprehensive understanding of when and how 5f orbitals participate in complex chemical bonding is important for a variety of applications. The actinides are unique in that they possess 5f orbitals and can access high oxidation states, which make them attractive for use in catalysis. Fundamental studies of actinide-ligand interactions offer a mechanism to examine the activation of the 5f orbitals so that the selectivity of 5f orbitals can be assessed. A previous study examined the reaction of Pu + + CO 2 and determined that the reaction efficiency is restricted by a barrier, namely, promotion from the Pu + ground-state configuration, 5f 6 7s, to a reactive-state configuration, 5f 5 6d 2 . The present study illustrates the benefit of activation of Pu's 5f orbitals when studying the reaction of Pu + + NO. In this reaction, PuO + forms in an exothermic, barrierless process. The 5f orbitals can and do participate in forming a linear intermediate, [N-Pu-O] + , and this drives the exothermic reaction. Understanding the conditions under which 5f orbitals are active in chemical bonding is the key to exploiting the actinides' selective catalytic capabilities.

A guided ion beam tandem mass spectrometer was used to study the reactions of U+ with N2 and NO. Reaction cross sections were measured over a wide range of energy for both systems. In each reaction, UN+ is formed by an endothermic process, thereby enabling the direct measurement of the threshold energy and determination of the UN+ bond dissociation energy. For the reaction of U+ + N2, a threshold energy (E0) of 4.02 ± 0.11 eV was measured, leading to D0 (UN+) = 5.73 ± 0.11 eV. The reaction of U+ + NO yields UO+ through an exothermic, barrierless process that proceeds with 94 ± 23% efficiency at the lowest energy. Analysis of the endothermic UN+ cross section in this reaction provides E0 = 0.72 ± 0.11 eV and, therefore, D0 (UN+) = 5.78 ± 0.11 eV. Averaging the values obtained from both reactions, we report D0 (UN+) = 5.76 ± 0.13 eV as our best value (uncertainty of two standard deviations). Combined with precise literature values for the ionization energies of U and UN, we also derive D0 (UN) = 5.86 ± 0.13 eV. Both bond dissociation energies agree well with high-level theoretical treatments in the literature. The formation of UN+ in reaction of U+ with NO also exhibits a considerable increase in reaction probability above ∼3 eV. Theory suggests that this may be consistent with the formation of UN+ in excited quintet spin states, which we hypothesize are dynamically favored because the number of 5f electrons in reactants and products is conserved., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

In a previous study, electrospray ionization, collision-induced dissociation (CID), and gas-phase ion-molecule reactions were used to create and characterize ions derived from homogeneous precursors composed of a uranyl cation (U VI O 2 2+ ) coordinated by either formate or acetate ligands [E. Perez, C. Hanley, S. Koehler, J. Pestok, N. Polonsky and M. Van Stipdonk, Gas phase reactions of ions derived from anionic uranyl formate and uranyl acetate complexes, J. Am. Soc. Mass Spectrom. , 2016, 27 , 1989-1998]. Here, we describe a follow-up study of anionic complexes that contain a mix of formate and acetate ligands, namely [UO 2 (O 2 C-CH 3 ) 2 (O 2 C-H)] - and [UO 2 (O 2 C-CH 3 )(O 2 C-H) 2 ] - . Initial CID of either anion causes decarboxylation of a formate ligand to create carboxylate-coordinated U-hydride product ions. Subsequent CID of the hydride species causes elimination of acetaldehyde or formaldehyde, consistent with reactions that include intra-complex hydride attack upon bound acetate or formate ligands, respectively. Density functional theory (DFT) calculations reproduce the experimental observations, including the favored elimination of formaldehyde over acetaldehyde by hydride attack during CID of [UO 2 (H)(O 2 C-CH 3 )(O 2 C-H)] - . We also discovered that MS n CID of the acetate-formate complexes leads to generation of the oxyl-methide species, [UO 2 (O)(CH 3 )] - , which reacts with H 2 O to generate [UO 2 (O)(OH)] - . DFT calculations support the observation that formation of [UO 2 (O)(OH)] - by elimination of CH 4 is favored over H 2 O addition and rearrangement to create [UO 2 (OH) 2 (CH 3 )] - .