In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes

Brewster, James T.; Mangel, Daniel N.; Gaunt, Andrew J.; Saunders, Douglas P.; Zafar, Hadiqa; Lynch, Vincent M.; Boreen, Michael A.; Garner, Mary E.; Goodwin, Conrad A.  P.; Settineri, Nicholas S.; Arnold, John; Sessler, Jonathan L.

doi:10.1021/jacs.9b09123

Title: In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes

Journal Article · Mon Oct 14 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b09123· OSTI ID:1615754

^[1]; Mangel, Daniel N. ^[1];

^[2]; Saunders, Douglas P. ^[1];

^[1]; Lynch, Vincent M. ^[1];

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Univ. of Texas, Austin, TX (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)

In our research, we report a first series of in-plane thorium(IV), uranium(IV), and neptunium(IV) expanded porphyrin complexes. These actinide (An) complexes were synthesized using a hexa-aza porphyrin analogue, termed dipyriamethyrin, and the non-aqueous An(IV) precur-sors: ThCl₄(DME)₂, UCl₄, and NpCl₄(DME)₂ under conditions of in situ sodium bis(trimethylsilyl)amide deprotonation. The molecu-lar and electronic structure of the ligand, each An(IV) complex, and a corresponding uranyl(VI) complex were characterized using NMR and UV-vis spectroscopies, as well as single crystal X-ray diffraction analysis. Computational analyses of these complexes, coupled with their structural features, provide support for the conclusion that a greater degree of covalency in the ligand-cation orbital interactions arises as the early actinide series is traversed from Th(IV) to U(IV) and Np(IV). The axial ligands in the current An(IV) complexes proved labile, allowing for the electronic features of these complexes to be further modified.

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Research Organization:: Univ. of Texas, Austin, TX (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-01ER15186

OSTI ID:: 1615754

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 44; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ligands
pyrroles
ions
covalent bonding
actinides

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