Complex Inorganic Actinide Materials

Marsh, Matthew L.; Albrecht‐Schmitt, Thomas E.

doi:10.1002/9781119115557.ch3

Cited by 1 publication

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“…In fact, few series have been established that extend from earlier actinides to those that lie beyond curium. These examples are largely restricted to halides, − triflates, − cyclopentadienylides, dithiocarbamates, , iodates, ,− hydroxypyridonates, , and borates, and even in these cases some of the compounds are quite historic and do not even vaguely meet modern standards of characterization. The situation is even more pronounced for complexes containing An 2+ cations beyond uranium .…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Studies of Selected Lanthanide and Californium Cryptates

et al. 2019

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Efforts to quantitatively reduce CfIII → CfII in solution as well as studies of its cyclic voltammetry have been hindered by its scarcity, significant challenges associated with manipulating an unusually intense γ emitter, small reaction scales, the need for nonaqueous solvents, and its radiolytic effects on ligands and solvents. In an effort to overcome these impediments, we report on the stabilization of CfII by encapsulation in 2.2.2-cryptand and comparisons with the readily reducible lanthanides, Sm3+, Eu3+, and Yb3+. Cyclic voltammetry measurements suggest that CfIII/II displays electrochemical behavior with characteristics of both SmIII/II and YbIII/II. The °E 1/2 values of −1.525 and −1.660 V (vs Fc/Fc+ in tetrahydrofuran (THF)) for [Cf(2.2.2-crypt)]3+/2+ and [Sm(2.2.2-crypt)]3+/2+, respectively, are similar. However, the ΔE values upon complexation by 2.2.2-cryptand for CfIII/II more closely parallels YbIII/II with postencapsulation shifts of 705 and 715 mV, respectively, whereas the shift of SmIII/II (520 mV) mirrors that of EuIII/II (524 mV). This suggests more structural similarities between CfII and YbII in solution than with SmII that likely originates from more similar ionic radii and local coordination environments, a supposition that is corroborated by crystallographic and extended X-ray absorption fine structure measurements from other systems. Competitive-ion binding experiments between EuIII/II, SmIII/II, and YbIII/II were also performed and show less favorable binding by YbIII/II. Connectivity structures of [Ln(2.2.2-cryptand)(THF)][BPh4]2 (Ln = EuII, SmII) are reported to show the important role that THF plays in these redox reactions.

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