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Abstract 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 twotrans‐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 U^VIoxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulatedexooxo and only one silylation is needed to enable migration of theendooxo out of the cone, whereupon a second silylation affords the stable U^IVcis‐bis(siloxide) [A]₂[U(OSiMe₃)₂(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putativecisdioxo isomer of [UO₂(TC4A)]²⁻would be stable if it could be accessed synthetically, at only 23 kcal.mol⁻¹in energy above the classicaltransdioxo. Calculations for the transuraniccis[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 acis‐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‐O_Argroups stabilizes the U=O ‘yl’ bonds, explaining the stability of the putativecis[UO₂(TC4A)]²⁻in this ligand framework. 

We report accelerated rates of oxygen-atom transfer from a polyoxovanadate–alkoxide cluster following functionalization with a 4- tert butylcalix[4]arene ligand. Incorporation of this electron withdrawing ligand modifies the electronics of the metal oxide core, favoring a mechanism in which the rate of oxygen-atom transfer is limited by outer-sphere electron transfer. 

We report the synthesis of a cyclic hexavanadate polyoxovanadate-alkoxide cluster, [VO(OC2H5)2]6 , and its conversion, under solvothermal conditions, to an oxygen-deficient Lindqvist assembly, [V 6 O 6 (OC 2 H 5 ) 12 ] n ( n = 1−, 0). This study presents insights into the mechanism of organo-functionalized polyoxovandate-alkoxide formation, namely identifying essential intermediates and the source of the central μ 6 -O 2− ligand. 

We report a rare example of oxygen atom transfer (OAT) from a polyoxometalate cluster to a series of tertiary phosphanes. Addition of PR 3 (PR 3 = PMe 3 , PMe 2 Ph, PMePh 2 , PPh 3 ) to a neutral methoxide-bridged polyoxovanadate-alkoxide (POV-alkoxide) cluster, [V 6 O 7 (OMe) 12 ] 0 , results in isolation of a reduced structure with phosphine oxide datively coordinated to a site-differentiated V III ion. A positive correlation between the steric and electronic properties of the phosphane and the reaction rate was observed. Further investigation of the steric influence of the alkoxy-bridged clusters on OAT was probed through the use of POV clusters with bridging alkoxide ligands of varying chain length ([V 6 O 7 (OR′) 12 ]; R′ = Et, n Pr). These investigations expose that steric hinderance of the vanadyl moieties has significant influence on the rate of OAT. Finally, we report the reactivity of the reduced POV-alkoxide clusters with styrene oxide, resulting in the deoxygenation of the substrate to generate styrene. This result is the first example of epoxide deoxygenation using homometallic polyoxometalate clusters, demonstrating the potential for mono-vacant Lindqvist clusters to catalyze the removal of oxygen atoms from organic substrates. 

Abstract A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron‐functionalized and hexavanadium polyoxovanadate‐alkoxide clusters, which we characterized here using V K‐edge X‐ray absorption spectroscopy. Substantial changes in the pre‐edge peak intensities were observed that tracked with the V 3d‐electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the Fe^IIIcations were electronically isolated from the polyoxovanadate core.