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Synthesis and Hydrolysis of Uranyl, Neptunyl, and Plutonyl Gas-Phase Complexes Exhibiting Discrete Actinide–Carbon Bonds

Journal Article · · Organometallics
 [1];  [1];  [1];  [2];  [3];  [1];  [4];  [5];  [6];  [7];  [7];  [8];  [7];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Universita della Calabria (Italy). Dipartimento di Chimica
  3. Universidade de Lisboa (Portugal). Centro de Ciencias e Tecnologias Nucleares, Instituto Superior Tecnico
  4. Skyline College, San Bruno, CA (United States)
  5. Duquesne University, Pittsburgh, PA (United States). Department of Chemistry and Biochemistry
  6. Duquesne University, Pittsburgh, PA (United States). Department of Physics
  7. FELIX Laboratory (The Netherlands). Radboud University, Institute for Molecules and Materials
  8. FELIX Laboratory (The Netherlands). Radboud University, Institute for Molecules and Materials ; University of Amsterdam (The Netherlands). vant Hoff Institute for Molecular Sciences
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In this study, gas-phase organoactinyl complexes possessing discrete An–C bonds (An = U, Np, Pu) were synthesized in a quadrupole ion trap by endothermic decarboxylation of [AnO2(O2C–R)3]- anion complexes in which a formally AnO22+ actinyl core is coordinated by three carboxylate ligands, with R = CH3 (methyl), CH3CC (1-propynyl), C6H5 (phenyl), C6F5 (pentafluorophenyl). Decarboxylation and competing ligand loss were studied computationally by density functional theory complementing experiment. Although decarboxylation was computed to be the energetically most favorable process in all cases, reduction from An(VI) to An(V) via neutral ligand loss was often prevalent, particularly for An = Np, Pu, presumably resulting from barriers associated with decarboxylation. Comparative hydrolysis rates of the An–C bonds were experimentally determined, and the chemical properties of these bonds were analyzed by the quantum theory of atoms in molecules. The measured hydrolysis rates differed by up to 3 orders of magnitude: the fastest was for [(CH3CC)UO2(O2C–CCCH3)2]- and the slowest for [(C6F5)PuO2(O2C–C6F5)2]-. There is a general correlation between hydrolysis exothermicity and hydrolysis rate. Prototypical hydrolysis reaction pathways computed for R = CH3 (An = U, Np) reveal a mechanism in which an outer-sphere water becomes inner-sphere concomitant with transfer of an H atom to yield an OH ligand and CH4, with a net energy release of 170 kJ mol–1 and a transition state barrier of 45 kJ mol–1 for An = U. Infrared multiphoton dissociation spectra of selected complexes were acquired to confirm the predicted structures by agreement between the computed and observed vibrational frequencies. Lastly, the experiment and theory results provide an evaluation of the comparative propensities for formation of the organoactinyls as a function of actinide and carboxylate and an assessment of the nature and stability toward hydrolysis of the primarily ionic An–C bonds.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS) (SC-27)
DOE Contract Number:
AC02-05CH11231
OSTI ID:
1379332
Journal Information:
Organometallics, Journal Name: Organometallics Journal Issue: 9 Vol. 35; ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY