Carbon-Sulfur Bond Strength in Methanesulfinate and Benzenesulfinate Ligands Directs Decomposition of Np(V) and Pu(V) Coordination Complexes - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Dalton Transactions Année : 2020

Carbon-Sulfur Bond Strength in Methanesulfinate and Benzenesulfinate Ligands Directs Decomposition of Np(V) and Pu(V) Coordination Complexes

Résumé

Gas-phase coordination complexes of actinyl(V) cations, AnO2+, provide a basis to assess fundamental aspects of actinide chemistry. Electrospray ionization of solutions containing an actinyl cation and sulfonate anion CH3SO2- or C6H5SO2- generated complexes [(AnVO2)(CH3SO2)2]- or [(AnVO2)(C6H5SO2)2]- where An = Np or Pu. Collision induced dissociation resulted in C-S bond cleavage for methanesulfinate to yield [(AnVO2)(CH3SO2)(SO2)]-, whereas hydrolytic ligand elimination occurred for benzenesulfinate to yield [(AnVO2)(C6H5SO2)(OH)]-. These different fragmentation pathways are attributed to a stronger C6H5-SO2- versus CH3-SO2- bond, which was confirmed for both the bare and coordinating sulfinate anions by energies computed using a relativistic multireference perturbative approach (XMS-CASPT2 with spin-orbit coupling). The results demonstrate shutting off a ligand fragmentation channel by increasing the strength of a particular bond, here a sulfinate C-S bond. The [(AnVO2)(CH3SO2)(SO2)]- complexes produced by CID spontaneously react with O2 to eliminate SO2, yielding [(AnO2)(CH3SO2)(O2)]-, a process previously reported for An = U and found here for An = Np and Pu. Computations confirm that the O2/SO2 displacement reactions should be exothermic or thermoneutral for all three An, as was experimentally established. The computations furthermore reveal that the products are superoxides [(AnVO2)(CH3SO2)(O2)]- for An = Np and Pu, but peroxide [(UVIO2)(CH3SO2)(O2)]-. Distinctive reduction of O2- to O22- concomitant with oxidation of U(V) to U(VI) reflects the relatively higher stability of hexavalent uranium versus neptunium and plutonium.
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Dates et versions

hal-02486581 , version 1 (04-10-2021)

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Citer

Valérie Vallet, Yu Gong, Mohammad Saab, Florent Réal, John Gibson. Carbon-Sulfur Bond Strength in Methanesulfinate and Benzenesulfinate Ligands Directs Decomposition of Np(V) and Pu(V) Coordination Complexes. Dalton Transactions, 2020, 49 (10), pp.3293-3303. ⟨10.1039/d0dt00125b⟩. ⟨hal-02486581⟩
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