George Kathryn, Muller Julie, Berthon Laurence, Berthon Claude, Guillaumont Dominique, Vitorica-Yrezabal Iñigo J, Stafford H Victoria, Natrajan Louise S, Tamain Christelle
The Centre for Radiochemistry Research, School of Chemistry , The University of Manchester , Oxford Road , Manchester M13 9PL , United Kingdom.
Nuclear Energy Division, RadioChemistry & Processes Department , CEA , Bagnols-sur-Cèze F-30207 , France.
Inorg Chem. 2019 May 20;58(10):6904-6917. doi: 10.1021/acs.inorgchem.9b00346. Epub 2019 Apr 26.
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 [NBu][Pu(NO)] yields the respective Pu complexes [Pu(TPIP)(NO)] and [Pu(TIPIP)(NO)] + [Pu(TIPIP)(NO)]. Similarly, the reactions of NaTPIP and NaTIPIP with a Pu(VI) nitrate solution lead to the formation of [PuO(HTIPIP)(HO)][NO], which incorporates a protonated bidentate TIPIP ligand, and [PuO(TPIP)(HTPIP)(NO)], where the protonated HTPIP ligand is bound in a monodentate fashion. Finally, a mixed U(VI)/Pu(VI) compound, [(UO/PuO)(TPIP)(HTPIP)(NO)], 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 Pr) on the nature of the complex is discussed with the help of DFT studies.
报道了钚（IV）和钚（VI）与络合剂四苯基和四异丙基亚氨基二膦酸酯（TPIP和TIPIP）的配位化学。用四丁基铵硝酸钚（[NBu][Pu(NO)]）处理四苯基亚氨基二膦酸钠（NaTPIP）及其带有外围异丙基的对应物（NaTIPIP），得到相应的钚配合物[Pu(TPIP)(NO)]和[Pu(TIPIP)(NO)] + [Pu(TIPIP)(NO)]。同样，NaTPIP和NaTIPIP与硝酸钚（VI）溶液反应生成[PuO(HTIPIP)(HO)][NO]，其中包含一个质子化的双齿TIPIP配体，以及[PuO(TPIP)(HTPIP)(NO)]，其中质子化的HTPIP配体以单齿方式结合。最后，报道了一种混合的铀（VI）/钚（VI）化合物[(UO/PuO)(TPIP)(HTPIP)(NO)]。所有这些酰基配合物在溶液中数周内都保持在+VI氧化态。通过结合X射线结构研究、核磁共振、光学、振动光谱和电喷雾电离质谱对所得配合物进行了表征。借助密度泛函理论研究讨论了R基团（R = 苯基或丙基）对配合物性质的影响。
