Halide abstraction from halogenated acetate ligands by actinyls: a competition between bond breaking and bond making

The Journal of Physical Chemistry. a
Phuong D Dau, John K Gibson

Abstract

Transfer of halogen atoms from halogenated acetate ligands, CX3CO2 (X = F, Cl, Br), to actinyls, AnO2(2+) (An = U, Np, Pu) is stimulated by collision-induced dissociation (CID) in a quadrupole ion trap. CID of [AnO2(CF3CO2)3](-) complexes results exclusively in F atom transfer, concomitant with elimination of CF2CO2, to produce [(CF3CO2)2AnO2F](-), [(CF3CO2)AnO2F2](-), and [AnO2F3](-). This contrasts with CID of transition metal fluoroacetates for which CO2-elimination to produce organometallics is an important pathway, a disparity that can be attributed to the differing bond dissociation energies (BDEs) of the created metal-carbon and metal-fluorine bonds. The dominant pathway for CID of [AnO2(CF3CO2)(CCl3CO2)(CBr3CO2)](-) is Br-atom transfer to produce [(CF3CO2)(CCl3CO2)AnO2Br](-). The preferential formation of bromides, despite that the BDEs of An-F bonds are substantially greater than those of An-Br bonds, is attributed to the offsetting effect of higher BDEs for C-F versus C-Br bonds. The results for the trihaloacetates are similar for uranyl, neptunyl and plutonyl, indicating that for all three the An-X bond dissociation energies are sufficiently high that X atom transfer is overwhelmingly dominant. CID of [UO2(CH2XCO2)2(...Continue Reading

References

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Jan 15, 2013·The Journal of Physical Chemistry. a·Yu Gong, John K Gibson
Feb 28, 2014·The Journal of Physical Chemistry. a·Ana F LucenaJohn K Gibson

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Citations

Mar 16, 2017·Inorganic Chemistry·Phuong D DauJohn K Gibson
Sep 3, 2019·Physical Chemistry Chemical Physics : PCCP·Thibault CheissonEric J Schelter
Apr 14, 2019·Journal of the American Society for Mass Spectrometry·Davide CorintiDomenico Osella

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