Controlled Deprotection and Reorganization of Uranyl Oxo Groups in a Binuclear Macrocyclic Environment

Abstract

Anschalten der UV‐Reaktivität: Der silylierte Dioxouran(V)‐Komplex [(Me3SiOUO)2(L)2] (A) ist inert gegen Oxidation, kann aber nach Zweielektronenreduktion zu [(Me3SiOUO)2(L)]2− (1) zu [OU(μ‐O)2UO(L)2]2− (2) mit wiederhergestelltem Uranylcharakter desilyliert werden. Beim Entfernen der Silylgruppe zeigt sich eine neue Redox‐ und Oxoumlagerungschemie des Urans unter Rückbildung des Uranylmotivs sowie der Beteiligung des UVI/V‐Paars an einer Disauerstoffreduktion.

The Energy Landscape of Uranyl–Peroxide Species

“…In contrast, alkali uranyl-peroxide formation from the oxides features highly exothermic enthalpies of formation from the oxides plus oxygen (DH o f,ox ); [4a] and these phases remain thermodynamically stable to spontaneous decomposition with the evolution of oxygen, even in the absence of excess peroxide in the aqueous solution. Thus, it is even thermodynamically favorable to form them from UO 2 in the absence of peroxide; [5] rather atmospheric oxygen can be reduced to peroxide, whereas U 4 + is oxidized to U 6 + , although the details of such a process have not been elucidated.…”

Tuning electronic structures of uranyl fluorides via increasing equatorial pyridyl number and extending pyridyl conjugation

“…Usually, the linear uranyl cation is equatorially coordinated by 4 to 6 ligands. [17][18][19][20][21][22][23] A great number of donors [19][20][21][22][23][24][25][26][27][28][29][30][31][32] such as nitrogen (pyridine, polypyridine, porphyrin, expanded porphyrin and calixpyrroles), oxygen (THF) and halogen have been attempted for uranyl complexation. These experimentally synthesized complexes as well as their characterization and relevant theoretical computations have provided an insight into their electronic structures and physicochemical properties [9][10][11]13].…”