A Pseudotetrahedral Uranium(V) Complex

doi:10.1021/acs.inorgchem.7b03139

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 then 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.

Authors:

^[1]; Duignan, Thomas J. ^[2];

^[1]; Fleischauer, Valerie E. ^[3];

^[4];

^[1];

^[3];

^[1];

^[1]

Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. at Buffalo, NY (United States). Dept. of Chemistry
Univ. of Rochester, NY (United States). Dept. of Chemistry
Univ. at Buffalo, NY (United States). Dept. of Chemistry

Publication Date:: 2018-07-05

Research Org.:: Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1460655

Report Number(s):: LA-UR-18-21979
Journal ID: ISSN 0020-1669; TRN: US1901890

Grant/Contract Number:: AC52-06NA25396; SC0016002; SC0001136; AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Volume: 57; Journal Issue: 14; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY

Citation Formats


                    Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., and Yang, Ping. A Pseudotetrahedral Uranium(V) Complex.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.inorgchem.7b03139.

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                    Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., & Yang, Ping. A Pseudotetrahedral Uranium(V) Complex.  United States.  doi:10.1021/acs.inorgchem.7b03139.

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                    Tondreau, Aaron M., Duignan, Thomas J., Stein, Benjamin W., Fleischauer, Valerie E., Autschbach, Jochen, Batista, Enrique R., Boncella, James M., Ferrier, Maryline G., Kozimor, Stosh A., Mocko, Veronika, Neidig, Michael L., Cary, Samantha K., and Yang, Ping. Thu .  
        "A Pseudotetrahedral Uranium(V) Complex".  United States.  doi:10.1021/acs.inorgchem.7b03139.  https://www.osti.gov/servlets/purl/1460655.

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@article{osti_1460655,

  title        = {A Pseudotetrahedral Uranium(V) Complex},

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

  abstractNote = {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 then 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.},

  doi          = {10.1021/acs.inorgchem.7b03139},

  journal      = {Inorganic Chemistry},

  number       = 14,

  volume       = 57,

  place        = {United States},

  year         = {2018},

  month        = {7}

}

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DOI: 10.1021/acs.inorgchem.7b03139

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Works referencing / citing this record:

CCDC 1589613: Experimental Crystal Structure Determination: RIFSEH : bis(μ-chloro)-tris(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-uranium
dataset, December 2017

Tondreau, Aaron; Duignan, Thomas; Stein, Benjamin
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1qc3v1

CCDC 1589614: Experimental Crystal Structure Determination: RIFSIL : tetrakis(cyclohexyl(trimethylsilyl)amino)-uranium
dataset, December 2017

Tondreau, Aaron; Duignan, Thomas; Stein, Benjamin
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1qc3w2

CCDC 1589615: Experimental Crystal Structure Determination: RIFWAH : tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-uranium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate fluorobenzene solvate
dataset, April 2018

Tondreau, Aaron; Duignan, Thomas; Stein, Benjamin
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1qc3x3

CCDC 1589616: Experimental Crystal Structure Determination: RIFVUA : pentakis(μ-chloro)-tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-di-uranium
dataset, April 2018

Tondreau, Aaron; Duignan, Thomas; Stein, Benjamin
Cambridge Structural Database (CSD)
DOI: 10.5517/ccdc.csd.cc1qc3y4

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Title: A Pseudotetrahedral Uranium(V) Complex

Abstract

Citation Formats

CCDC 1589613: Experimental Crystal Structure Determination: RIFSEH : bis(μ-chloro)-tris(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-uranium dataset, December 2017

CCDC 1589614: Experimental Crystal Structure Determination: RIFSIL : tetrakis(cyclohexyl(trimethylsilyl)amino)-uranium dataset, December 2017

CCDC 1589615: Experimental Crystal Structure Determination: RIFWAH : tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-uranium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate fluorobenzene solvate dataset, April 2018

CCDC 1589616: Experimental Crystal Structure Determination: RIFVUA : pentakis(μ-chloro)-tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-di-uranium dataset, April 2018

CCDC 1589613: Experimental Crystal Structure Determination: RIFSEH : bis(μ-chloro)-tris(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-uranium
dataset, December 2017

CCDC 1589614: Experimental Crystal Structure Determination: RIFSIL : tetrakis(cyclohexyl(trimethylsilyl)amino)-uranium
dataset, December 2017

CCDC 1589615: Experimental Crystal Structure Determination: RIFWAH : tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-uranium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate fluorobenzene solvate
dataset, April 2018

CCDC 1589616: Experimental Crystal Structure Determination: RIFVUA : pentakis(μ-chloro)-tetrakis(N-cyclohexyl-1,1,1-trimethylsilanaminato)-bis(tetrahydrofuran)-lithium-di-uranium
dataset, April 2018