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Pacman‐Like Alkaliated Actinyl Complexes of a Polypyrrolic Macrocycle: A Relativistic DFT Study
Author(s) -
Bi YanTing,
Zhong YuXi,
Zhou BaiBin,
Pan QingJiang
Publication year - 2017
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.201700391
Subject(s) - uranyl , chemistry , alkali metal , lithium (medication) , density functional theory , redox , exothermic reaction , oxidative addition , molecule , hydrogen bond , actinide , crystallography , inorganic chemistry , computational chemistry , organic chemistry , catalysis , ion , medicine , endocrinology
A series of doubly alkaliated actinyl complexes, [(thf)(An m O 2 )(A 2 L)] n– ( An m ‐A ; An=U, Np and Pu; m=VI and n=0; m=V and n=1; A=Li, Na and K; L is an octadentate polypyrrolic tetraanion) have been investigated for their structures, transformation reaction energies and redox property using relativistic density functional theory. The study confirms experimental results of the synthesized lithiated uranyl complexes and the proposed potassiated uranyl ones, and furthermore extends to more toxic and radioactive transuranics that are difficultly handled in experiment. Comparison with hydrogen analogues, [(thf)(An m O 2 )(H 2 L)] n– ( An m ‐H ), finds that the introduction of alkali atoms lengthens An=O endo and An=O exo bonds. Transformation reaction of An m ‐A (A=Li, Na and K) starting from the respective An m ‐H was calculated to be exothermic. The alkaliated complex shows more positive reduction potential in most cases. All the results unravel the alkali‐mediated activation on the inert uranyl(VI) U=O bonding; the lithium complex, for instance, possesses the largest reduction potential (E 0 corr ), which indicates the strongest lithium activation. Further comparison was also made with the alkaliated uranyl complexes where the alkali metals are saturated by thf molecules.