Exploring the Coordination of Plutonium and Mixed Plutonyl-Uranyl Complexes of Imidodiphosphinates.
Kathryn GeorgeJulie MullerLaurence BerthonClaude BerthonDominique GuillaumontIñigo J Vitorica-YrezabalH Victoria StaffordLouise S NatrajanChristelle TamainPublished in: Inorganic chemistry (2019)
The coordination chemistry of plutonium(IV) and plutonium(VI) with the complexing agents tetraphenyl and tetra-isopropyl imidodiphosphinate (TPIP- and TIPIP-) is reported. Treatment of sodium tetraphenylimidodiphosphinate (NaTPIP) and its related counterpart with peripheral isopropyl groups (NaTIPIP) with [NBu4]2[PuIV(NO3)6] yields the respective PuIV complexes [Pu(TPIP)3(NO3)] and [Pu(TIPIP)2(NO3)2] + [PuIV(TIPIP)3(NO3)]. Similarly, the reactions of NaTPIP and NaTIPIP with a Pu(VI) nitrate solution lead to the formation of [PuO2(HTIPIP)2(H2O)][NO3]2, which incorporates a protonated bidentate TIPIP- ligand, and [PuO2(TPIP)(HTPIP)(NO3)], where the protonated HTPIP ligand is bound in a monodentate fashion. Finally, a mixed U(VI)/Pu(VI) compound, [(UO2/PuO2)(TPIP)(HTPIP)(NO3)], is reported. All these actinyl complexes remain in the +VI oxidation state in solution over several weeks. The resultant complexes have been characterized using a combination of X-ray structural studies, NMR, optical, vibrational spectroscopies, and electrospray ionization mass spectrometry. The influence of the R-group (R = phenyl or iPr) on the nature of the complex is discussed with the help of DFT studies.
Keyphrases
- high resolution
- mass spectrometry
- magnetic resonance
- density functional theory
- magnetic resonance imaging
- solid state
- hydrogen peroxide
- drinking water
- liquid chromatography
- computed tomography
- high speed
- capillary electrophoresis
- ms ms
- preterm birth
- drug induced
- high performance liquid chromatography
- electron transfer