Redox behavior of gas phase Pu(IV)-monodentate ligand complexes: an investigation by electrospray ionization mass spectrometry

Abstract

This study reports the gas phase complexation behavior of Pu(IV) with N,N-dialkylamide ligands and tributylphosphate by electrospray ionization mass spectrometry. In-source collision induced dissociation (CID) and ion trap collision induced dissociation were used to investigate the kinetic stability of Pu species in the gas phase. With both class of ligands, N,N-dialkylamide and trialkylphosphate, oxidation of Pu from the tetravalent state to the hexavalent state was observed at both high skimmer voltages and during ion trap CID. The results suggest that oxidation is due to the presence of a nitrate group in the coordination sphere of the metal and is independent of the ligand.

Effect of metal complexation on diglycolamide radiolysis: a comparison between ex situ gamma and in situ alpha irradiation

“…ESI-MS generally used to identify organic compounds in solution can also be used to probe metallic complexes existing in solution. 60,[83][84][85][86][87][88][89][90][91][92][93][94][95] The ESI-MS spectrum was collected for each TODGA-Am solution in order to identify the species coming from the free ligand or being involved in metallic complexes. The main species identified before degradation in these systems are the free ligand and Am spcies.…”

Exploring the Coordination of Plutonium and Mixed Plutonyl–Uranyl Complexes of Imidodiphosphinates

“…64−70 The publications range from species identification to specific interest in the chemistry of the f-elements 59,50,71 through the investigation of competitive interactions. 54 Pu(III), 61,59,60 Pu(IV) gas phase behavior 59,78 and Rios et al reported the gas phase reduction of PuO 2 2+ to Pu(V) and Pu(IV) followed by ESI-MS. 67 The ESI-MS spectra in positive ionization mode of 1 after dissolution of some crystals in THF and 1/1000 dilution in CH 3 CN are reported in the Figures S5 and S6. The main peak corresponds to [Pu(TPIP) 3 ] + (m/z = 1488.5).…”

“…This technique is known to be used in combination with traditional solution chemistry techniques to investigate metal–ligand interactions. , Actinide species have been studied by ESI-MS since the early 1990s where the use of electrospray mass spectrometry was utilized for the analysis of various elements including U­(VI), , Th­(IV), − Am­(III), ,− Np and Pu in different oxidation states. − The publications range from species identification to specific interest in the chemistry of the f-elements ,, through the investigation of competitive interactions . Additionally, a number of studies have included the use of ESI-MS to investigate the gas phase behavior of UO 2 + , UO 2 2+ , PuO 2 + and PuO 2 2+ ,,− ,− Pu­(III), ,, Pu­(IV) gas phase behavior , and Rios et al reported the gas phase reduction of PuO 2 2+ to Pu­(V) and Pu­(IV) followed by ESI-MS . The ESI-MS spectra in positive ionization mode of 1 after dissolution of some crystals in THF and 1/1000 dilution in CH 3 CN are reported in the Figures S5 and S6.…”