The propensities for organometallic complexes to hydrolyze is generally evaluated qualitatively, such as �highly moisture sensitive.�  In this work we quantitatively assess the comparative susceptibilities of selected organometallic complexes towards hydrolysis in the gas-phase.  Actinyl carboxylate anion complexes AnO2(RCOO)3- comprising the ubiquitous actinyl moiety, AnO22+ (An = U, Np, Pu), are produced by electrospray ionization and isolated in a quadrupole ion trap mass spectrometer (QIT/MS).  Decarboxylation by energetic collision induced dissociation of these complexes results in organoactinyl complexes according to Equation 1.            AnO2(RCOO)3- + ?E  ?  AnO2R(RCOO)2- + CO2                            (1)The resulting organoactinyl complex with an An-R bond is isolated in the QIT and exposed to different pressures of water (P[H2O] ~ 1-10 � 10-6 Torr) for varying reaction periods (trxn ~ 0.1-10 s) to evaluate hydrolysis rates under thermal reaction conditions, Equation 2.            AnO2R(RCOO)2- + H2O ?  AnO2(OH)(RCOO)2- + HR                   (2)Relative rates for Equation 2 provide a direct measure of the susceptibilities of the organoactinyls towards hydrolysis.  Results are compared for different actinides�U, Np and Pu�as well as for various organic ligands -R, such as -CH3, -C=C-CH3 and -C6H5.  The experimental results are evaluated by density functional computations of the observed hydrolysis processes.  A goal is to provide a basis to assess the intrinsic stabilities of organoactinide bonds, and potentially provide guidance for condensed phase synthetic approaches.*Supported by the U.S. Department of Energy, Basic Energy Sciences Heavy Element Chemistry and Community College Internship programs, and by Universit� della Calabria.

Hydrolysis of gas-phase organoactinide(VI) complexes<sup>
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248th National Meeting (2014)

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