Oligomers Intermediates in Between Two New Distinct Homonuclear Uranium(IV) DOTP Complexes** (original) (raw)

Chemistry – A European Journal, 2021

Abstract

Two new aqueous UIV complexes were synthesized by the interaction between the tetravalent uranium cation and the (1,4,7,10‐Tetraazacyclododecane‐1,4,7,10‐tetra(methylene phosphonic acid) (DOTP) macrocyclic ligand. Two distinct homonuclear complexes were identified; the first was characterized by X‐ray crystallography as a unique “out‐of‐cage”, [U(DOTPH6)2] complex, in which the UIV cation is octa‐coordinated to 4 phosphonic arms from each ligand in a square anti‐prism geometry, with a C4 symmetry. The second is the “in‐cage” [U(DOTPH4)] complex, in which the tetravalent cation is located between the macrocycle O4 and N4 planes. With the help of UV‐Vis absorption, 1H/31P NMR, ATR‐IR, and MALDI‐TOFMS analytical techniques, the chemical interchange between both species is presented. It is shown that the one‐way transition is governed by the formation of a multiple number of soluble oligomeric species consisting of varied stoichiometric ratios of both characterized homonuclear complexes.

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