Ligand‐Directed Actinide Oxo‐Bond Manipulation in Actinyl Thiacalix[4]arene Complexes.

Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO22+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An=U, Np, Pu). The thioether calixarene TC4A (4‐tert‐butyltetrathiacalix[4]arene) binds equatorially to the actinyl cation forming a conical pocket that differentiates the two trans‐oxo groups. The 'ate' complexes, [A]2[UO2(TC4A)] (A=[Li(DME)2], HNEt3) and [HNEt3]2[AnO2(TC4A)] (An=U, Np, Pu), enable selective oxo chemistry. Silylation of the UVI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable UIVcis‐bis(siloxide) [A]2[U(OSiMe3)2(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO2(TC4A)]2− would be stable if it could be accessed synthetically, at only 23 kcal.mol−1 in energy above the classical trans dioxo. Calculations for the transuranic cis[AnO2(TC4A)]2− (An=Np, Pu) are at higher energies, 30–35 kcal.mol−1, retaining the U complexes as the more obvious target for a cis‐dioxo actinyl ion. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as‐yet unseen uranyl geometry as further bonding in the TC4A U‐OAr groups stabilizes the U=O 'yl' bonds, explaining the stability of the putative cis[UO2(TC4A)]2− in this ligand framework. [ABSTRACT FROM AUTHOR]