TY - JOUR
T1 - In-Plane Thorium(IV), Uranium(IV), and Neptunium(IV) Expanded Porphyrin Complexes
AU - Brewster, James T.
AU - Mangel, Daniel N.
AU - Gaunt, Andrew J.
AU - Saunders, Douglas P.
AU - Zafar, Hadiqa
AU - Lynch, Vincent M.
AU - Boreen, Michael A.
AU - Garner, Mary E.
AU - Goodwin, Conrad A.P.
AU - Settineri, Nicholas S.
AU - Arnold, John
AU - Sessler, Jonathan L.
N1 - Funding Information:
Support for the work at UT Austin was provided by the U.S. Department of Energy, Office of Basic Energy Sciences (grant DE-FG02-01ER15186 to J.L.S.). Further support from the Robert A. Welch Foundation (F-0018 to J.L.S.) is gratefully acknowledged. The work at UC Berkeley was supported by the Director, Office of Science, Office of Basic Energy Sciences Division of Chemical Science, Geosciences, and Biosciences Heavy Element Chemistry Program of the U.S. Department of Energy (DOE) at Lawrence Berkeley National Laboratory under Contract DE-AC02-05CH11231. Experimental neptunium (Np) work was conducted at the Los Alamos National Laboratory (LANL) and we thank the Laboratory Directed Research and Development (LDRD) program for a Glenn T. Seaborg Graduate Summer Student Fellowship (J.T.B.) and a J. R. Oppenheimer Distinguished Postdoctoral Fellowship (C.A.P.G.), and U.S. DOE, Office of Science Office of Basic Energy Sciences, Division of Chemical Science, Geosciences and Biosciences, Heavy Element Chemistry Program at LANL (A.J.G.; contract DE-AC52-06NA25396). We thank Environmental Science Institute at The University of Texas at Austin for a Scientist in Residence Fellowship (J.T.B.).
Funding Information:
Support for the work at UT Austin was provided by the U.S. Department of Energy, Office of Basic Energy Sciences (grant DE-FG02–01ER15186 to J.L.S.). Further support from the Robert A. Welch Foundation (F-0018 to J.L.S.) is gratefully acknowledged. The work at UC Berkeley was supported by the Director, Office of Science, Office of Basic Energy Sciences, Division of Chemical Science, Geosciences, and Biosciences Heavy Element Chemistry Program of the U.S. Department of Energy (DOE) at Lawrence Berkeley National Laboratory under Contract DE-AC02–05CH11231. Experimental neptunium (Np) work was conducted at the Los Alamos National Laboratory (LANL) and we thank the Laboratory Directed Research and Development (LDRD) program for a Glenn T. Seaborg Graduate Summer Student Fellowship (J.T.B.) and a J. R. Oppenheimer Distinguished Postdoctoral Fellowship (C.A.P.G.), and U.S. DOE, Office of Science, Office of Basic Energy Sciences, Division of Chemical Science, Geosciences, and Biosciences, Heavy Element Chemistry Program at LANL (A.J.G.; contract DE-AC52–06NA25396). We thank Environmental Science Institute at The University of Texas at Austin for a Scientist in Residence Fellowship (J.T.B.).
Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/11/6
Y1 - 2019/11/6
N2 - Here we report the 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 nonaqueous An(IV) precursors, ThCl4(DME)2, UCl4, and NpCl4(DME)2. The molecular and electronic structures of the ligand, each An(IV) complex, and a corresponding uranyl(VI) complex were characterized using nuclear magnetic resonance (NMR) and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. Computational analyses of these complexes, coupled to 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 present An(IV) complexes proved labile, allowing for the electronic features of these complexes to be further modified.
AB - Here we report the 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 nonaqueous An(IV) precursors, ThCl4(DME)2, UCl4, and NpCl4(DME)2. The molecular and electronic structures of the ligand, each An(IV) complex, and a corresponding uranyl(VI) complex were characterized using nuclear magnetic resonance (NMR) and UV-vis spectroscopies as well as single-crystal X-ray diffraction analysis. Computational analyses of these complexes, coupled to 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 present An(IV) complexes proved labile, allowing for the electronic features of these complexes to be further modified.
UR - http://www.scopus.com/inward/record.url?scp=85074231780&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b09123
DO - 10.1021/jacs.9b09123
M3 - Article
C2 - 31609114
AN - SCOPUS:85074231780
SN - 0002-7863
VL - 141
SP - 17867
EP - 17874
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 44
ER -