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3556823
Investigation of gas-phase acetate exchange of tetravalent thorium and plutonium complexes
Date
April 8, 2021
Fundamental gas-phase reactions of actinide complexes elucidate their chemistry. Gas-phase studies provide uniquely detailed information on underlying chemical properties that influence bond dissociation and activation. Ligand exchange for actinide-acetate complexes AnIVLx(OCOCH3)5-x- (An = Th, Pu; L = Cl, NO3), as shown by reaction (1) probes the effect of the metal center and its ligand environment on reactivity. Using deuterated acetic acid, DOCOCD3, as the exchange reagent allows determination of kinetics for this thermoneutral reaction.
AnLx(OCOCH3)5-x- + DOCOCD3 --> AnLx(OCOCH3)4-x(OCOCD3)- + DOCOCH3 (1)
By comparing reaction (1) for different actinide metals, as well as for different ligands (L), systematic variations in bonding and reactivity are assessed. Experimental results show that reaction (1) is more efficient for Th(NO3)(OCOCH3)4- versus Pu(NO3)(OCOCH3)4-. Density functional theory computations of the reaction potential energy profiles are in accord with the observed kinetics. Analysis of the reaction mechanism using a Distortion/Interaction-Activation Strain (DIAS) model suggest a less favorable Pu-ligand interaction energy as the underlying cause for diminished reactivity. The results and analysis reveal and elucidate different characteristic chemistry of Th(IV) and Pu(IV).
AnLx(OCOCH3)5-x- + DOCOCD3 --> AnLx(OCOCH3)4-x(OCOCD3)- + DOCOCH3 (1)
By comparing reaction (1) for different actinide metals, as well as for different ligands (L), systematic variations in bonding and reactivity are assessed. Experimental results show that reaction (1) is more efficient for Th(NO3)(OCOCH3)4- versus Pu(NO3)(OCOCH3)4-. Density functional theory computations of the reaction potential energy profiles are in accord with the observed kinetics. Analysis of the reaction mechanism using a Distortion/Interaction-Activation Strain (DIAS) model suggest a less favorable Pu-ligand interaction energy as the underlying cause for diminished reactivity. The results and analysis reveal and elucidate different characteristic chemistry of Th(IV) and Pu(IV).
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