Windorff Cory J, Goodwin Conrad A P, Sperling Joseph M, Albrecht-Schönzart Thomas E, Bai Zhuanling, Evans William J, Huffman Zachary K, Jeannin Renaud, Long Brian N, Mills David P, Poe Todd N, Ziller Joseph W
Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces, New Mexico 88003, United States.
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
Inorg Chem. 2023 Nov 6;62(44):18136-18149. doi: 10.1021/acs.inorgchem.3c02575. Epub 2023 Oct 24.
The pursuit of a trivalent plutonium halide phosphine oxide compound, e.g., "PuBr(OPR)," instead led to the isolation of the tetravalent -PuBr(OPCy), , compound by spontaneous oxidation of Pu. The donating nature of phosphine oxides has allowed the isolation and characterization of by crystallographic, multinuclear NMR, solid state, and solution phase UV-vis-NIR spectroscopic techniques. The presence of a putative plutonyl(VI) complex formulated as "-PuOBr(OPCy)" was also observed spectroscopically and tentatively by single-crystal X-ray diffraction as a cocrystal of . A series of -ThX(OPCy) (X = Cl, ; Br, ; I, ) complexes were synthesized for comparison to . The triphenylphosphine oxide, OPPh, complexes, -AnI(OPPh) (An = Th, ; U, , were also synthesized for comparison, completing the series -UX(OPPh) (X = Cl, Br, I), . To enable the synthesis of and , a new nonaqueous thorium iodide starting material, ThI(EtO), was synthesized. The syntheses of organic solvent soluble ThIL (L = EtO, OPCy, and OPPh) are the first examples of crystallographically characterized neutral thorium tetraiodide materials beyond binary ThI. To show the viability of ThI(EtO) as a starting material for organothorium chemistry, (CMeH)ThI was synthesized and crystallographically characterized.
对三价卤化钚氧化膦化合物（例如“PuBr(OPR)”）的研究，反而通过钚的自发氧化分离出了四价的PuBr(OPCy)₃化合物。氧化膦的给电子性质使得通过晶体学、多核核磁共振、固态和溶液相紫外 - 可见 - 近红外光谱技术对其进行分离和表征成为可能。还通过光谱观察到并通过单晶X射线衍射初步鉴定出一种假定的钚酰(VI)配合物，其化学式为“PuOBr(OPCy)”，是一种共晶体。合成了一系列ThX(OPCy)₃（X = Cl、Br、I）配合物用于与PuBr(OPCy)₃进行比较。还合成了三苯基氧化膦OPPh₃配合物AnI(OPPh)₃（An = Th、U）用于比较，从而完善了UX(OPPh)₃（X = Cl、Br、I）系列。为了能够合成PuBr(OPCy)₃和ThX(OPCy)₃，合成了一种新的非水碘化钍起始原料ThI₄(EtO)₂。有机溶剂可溶的ThI₄L（L = EtO、OPCy和OPPh）的合成是除二元ThI₄之外晶体学表征的中性四碘化钍材料的首个实例。为了证明ThI₄(EtO)₂作为有机钍化学起始原料的可行性，合成了(CMe₃H)₂ThI₄并对其进行了晶体学表征。
