Cation-Cation Interactions, Magnetic Communication, and Reactivity of the Pentavalent Uranium Ion U(NtBu)2+~

摘要

Pentavalent uranium complexes have long attracted attention as a means to probe the role of the f~1 electronic configuration in actinide chemistry. Studies of the UO3~+ ion have been essential to this area as a result of its role in nuclear fuel reprocessing, its speciation in the environment, and its potential to perform electrochemical catalysis. Despite this interest, well-characterized examples of the UO2~+ ion are exceedingly rare, which has limited their use to illustrate important fundamental concepts in actinide chemistry. Although some of the structurally characterized UO2~+ complexes are monomeric, many are oligomeric, for example, the uranyl(V) coordination polymer {UO2py5-KI2py2)_n the tetrameric complex UO2(dbm)24-K6py10·I2·py3 (py = pyridine, dbm = dibenzoylmethanate), and the dimeric complex {UO2(dbm)2K(18crown-6)}2. These oligomers demonstrate that the UO2~+ ion can assume many oxygen-bridged architectures. Although these complexes have been used to probe the role of cation-cation oligomeric interactions in structural uranyl(V) chemistry, very little is known about the reactivity and magnetic interactions between such f~1 actinide centers in polynuclear complexes. These properties can be further addressed by the study of other families of pentavalent actinide complexes that are similar in molecular and electronic structure to the UO2~+ ion.