In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes
Abstract
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.
- Authors:
-
[1];
[2];
[1];
[3];
[4];
[2];
[4];
[3];
[1]
- 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)
- Publication Date:
- Research Org.:
- Univ. of Texas, Austin, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1615754
- Grant/Contract Number:
- FG02-01ER15186
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 44; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ligands; pyrroles; ions; covalent bonding; actinides
Citation Formats
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, and Sessler, Jonathan L. In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b09123.
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. In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes. United States. https://doi.org/10.1021/jacs.9b09123
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, and Sessler, Jonathan L. Mon .
"In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes". United States. https://doi.org/10.1021/jacs.9b09123. https://www.osti.gov/servlets/purl/1615754.
@article{osti_1615754,
title = {In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes},
author = {Brewster, James T. and Mangel, Daniel N. and Gaunt, Andrew J. and Saunders, Douglas P. and Zafar, Hadiqa and Lynch, Vincent M. and Boreen, Michael A. and Garner, Mary E. and Goodwin, Conrad A. P. and Settineri, Nicholas S. and Arnold, John and Sessler, Jonathan L.},
abstractNote = {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.},
doi = {10.1021/jacs.9b09123},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 141,
place = {United States},
year = {Mon Oct 14 00:00:00 EDT 2019},
month = {Mon Oct 14 00:00:00 EDT 2019}
}
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Figures / Tables:
Figure 1: Representative expanded porphyrin-actinyl [An(V/VI)O2+/2+] complexes.
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