A Pseudotetrahedral Uranium(V) Complex

Aaron M. Tondreau; Thomas J. Duignan; Benjamin W. Stein; Valerie E. Fleischauer; Jochen Autschbach; Enrique R. Batista; James M. Boncella; Maryline G. Ferrier; Stosh A. Kozimor; Veronika Mocko; Michael L. Neidig; Samantha K. Cary; Ping Yang

doi:10.1021/acs.inorgchem.7b03139

A Pseudotetrahedral Uranium(V) Complex

Aaron M. Tondreau, Thomas J. Duignan, Benjamin W. Stein, Valerie E. Fleischauer, Jochen Autschbach, Enrique R. Batista, James M. Boncella, Maryline G. Ferrier, Stosh A. Kozimor, Veronika Mocko, Michael L. Neidig, Samantha K. Cary, Ping Yang

Research output: Contribution to journal › Article › peer-review

15 Scopus citations

Abstract

A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe₃)_x(Cl)_4-x, where x = 2, 3, or 4. The diamide was isolated as a bimetallic, bridging lithium chloride adduct ((UCl₂(NCyTMS)₂)₂-LiCl(THF)₂), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)₃-LiCl(THF)₂). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the U^V amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural U^IV and U^V tetraamide complexes. Spectroscopic investigations consisting of UV-vis, NIR, MCD, EPR, and U L₃-edge XANES, along with density functional and wave function calculations, of the four-coordinate U^IV and U^V complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.

Original language	English
Pages (from-to)	8106-8115
Number of pages	10
Journal	Inorganic Chemistry
Volume	57
Issue number	14
DOIs	https://doi.org/10.1021/acs.inorgchem.7b03139
State	Published - Jul 16 2018
Externally published	Yes

Funding

A.M.T., T.J.D., M.G.F., and B.W.S. thank the Glenn T. Seaborg Institute for support from a Seaborg Research Fellowship. Portions of this work (S.K.C.) were supported by a LANL Darleane Christian Hoffman Distinguished fellowship. M.L.N. gratefully acknowledges support from the U.S. Department of Energy, Office of Science, Early Career Research Program, via Grant DE-SC0016002. E.R.B. and P.Y. were supported by the Heavy Element Chemistry program at LANL sponsored by the U.S. Department of Energy Office of Basic Energy Sciences. J.A. acknowledges financial support from the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, via Grant DE-SC0001136 (formerly DE-FG02-09-ER16066). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-76SF00515. A.M.T. thanks Alejandro G. Lichtscheidl for assistance with electrochemistry and general helpful discussions. Los Alamos National Laboratory is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the U.S. Department of Energy under Contract DE-AC52-06NA25396. Seaborg Institute for support from a Seaborg Research Fellowship. Portions of this work (S.K.C.) were supported by a LANL Darleane Christian Hoffman Distinguished fellowship. M.L.N. gratefully acknowledges support from the U.S. Department of Energy, Office of Science, Early Career Research Program, via Grant DE-SC0016002. E.R.B. and P.Y. were supported by the Heavy Element Chemistry program at LANL sponsored by the U.S. Department of Energy Office of Basic Energy Sciences. J.A. acknowledges financial support from the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry program, via Grant DE-SC0001136 (formerly DE-FG02-09-ER16066). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-76SF00515. A.M.T. thanks Alejandro G. Lichtscheidl for assistance with electrochemistry and general helpful discussions. Los Alamos National Laboratory is operated by Los Alamos National Security, LLC, for the National Nuclear Security Administration of the U.S. Department of Energy under Contract DE-AC52-06NA25396.

Funders	Funder number
Glenn T. Seaborg Institute
LANL Darleane Christian Hoffman Distinguished fellowship
Office of Basic Energy Sciences	DE-FG02-09-ER16066, DE-SC0001136, DE-AC02-76SF00515
U.S. Department of Energy Office of Basic Energy Sciences
U.S. Department of Energy
Office of Science	DE-SC0016002
National Nuclear Security Administration	DE-AC52-06NA25396
Los Alamos National Laboratory

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title = "A Pseudotetrahedral Uranium(V) Complex",

abstract = "A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3)x(Cl)4-x, where x = 2, 3, or 4. The diamide was isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV-vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.",

author = "Tondreau, {Aaron M.} and Duignan, {Thomas J.} and Stein, {Benjamin W.} and Fleischauer, {Valerie E.} and Jochen Autschbach and Batista, {Enrique R.} and Boncella, {James M.} and Ferrier, {Maryline G.} and Kozimor, {Stosh A.} and Veronika Mocko and Neidig, {Michael L.} and Cary, {Samantha K.} and Ping Yang",

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doi = "10.1021/acs.inorgchem.7b03139",

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AU - Duignan, Thomas J.

AU - Stein, Benjamin W.

AU - Fleischauer, Valerie E.

AU - Autschbach, Jochen

AU - Batista, Enrique R.

AU - Boncella, James M.

AU - Ferrier, Maryline G.

AU - Kozimor, Stosh A.

AU - Mocko, Veronika

AU - Neidig, Michael L.

AU - Cary, Samantha K.

AU - Yang, Ping

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AB - A series of uranium amides were synthesized from N,N,N-cyclohexyl(trimethylsilyl)lithium amide [Li][N(TMS)Cy] and uranium tetrachloride to give U(NCySiMe3)x(Cl)4-x, where x = 2, 3, or 4. The diamide was isolated as a bimetallic, bridging lithium chloride adduct ((UCl2(NCyTMS)2)2-LiCl(THF)2), and the tris(amide) was isolated as the lithium chloride adduct of the monometallic species (UCl(NCyTMS)3-LiCl(THF)2). The tetraamide complex was isolated as the four-coordinate pseudotetrahedron. Cyclic voltammetry revealed an easily accessible reversible oxidation wave, and upon chemical oxidation, the UV amido cation was isolated in near-quantitative yields. The synthesis of this family of compounds allows a direct comparison of the electronic structure and properties of isostructural UIV and UV tetraamide complexes. Spectroscopic investigations consisting of UV-vis, NIR, MCD, EPR, and U L3-edge XANES, along with density functional and wave function calculations, of the four-coordinate UIV and UV complexes have been used to understand the electronic structure of these pseudotetrahedral complexes.

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A Pseudotetrahedral Uranium(V) Complex

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