Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

Alejandro G. Lichtscheidl; Justin K. Pagano; Brian L. Scott; Andrew T. Nelson; Jaqueline L. Kiplinger

doi:10.3390/inorganics4010001

Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et)

Alejandro G. Lichtscheidl, Justin K. Pagano, Brian L. Scott, Andrew T. Nelson, Jaqueline L. Kiplinger

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

6 Scopus citations

Abstract

The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C₅Me₄R)₂UCl₂ (R = Me, Et) with Me₃SiBr. Treatment of (C₅Me₄R)₂UCl₂ and (C₅Me₄R)₂UBr₂ (R = Me, Et) with K(O-2,6-ⁱPr₂C₆H₃) afforded the halide aryloxide mixed-ligand complexes (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(X) (R = Me, Et; X = Cl, Br). Complexes (C₅Me₄R)2U(O-2,6-ⁱPr₂C₆H₃)(Br) (R = Me, Et) can also be synthesized by treating (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Cl) (R = Me, Et) withMe₃SiBr, respectively. Reduction of (C₅Me₄R)₂UCl₂ and (C₅Me₄R)₂UBr₂ (R = Me, Et) with KC8 led to isolation of uranium(III) "ate" species [K(THF)][(C₅Me₅)₂UX₂] (X = Cl, Br) and [K(THF)0.5][(C₅Me₄Et)₂UX₂] (X = Cl, Br), which can be converted to the neutral complexes (C₅Me₄R)₂U[N(SiMe₃)₂] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.

Original language	English
Article number	17
Journal	Inorganics
Volume	4
Issue number	1
DOIs	https://doi.org/10.3390/inorganics4010001
State	Published - Mar 1 2016
Externally published	Yes

Funding

Acknowledgments: For financial support of this work, we acknowledge the U.S. Department of Energy through the Los Alamos National Laboratory (LANL) Laboratory Directed Research and Development (LDRD) Program and the Los Alamos National Laboratory Glenn Theodore Seaborg Institute for Transactinium Science (PD Fellowship to Alejandro G. Lichtscheidl), the Advanced Fuels Campaign Fuel Cycle Research & Development Program (Alejandro G. Lichtscheidl and Andrew T. Nelson), the Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program (Fellowship to Justin K. Pagano), and the Office of Basic Energy Sciences, Heavy Element Chemistry program (Jaqueline L. Kiplinger, Brian L. Scott, materials and supplies). The SCGSR program is administered by the Oak Ridge Institute for Science and Education for the DOE (contract DE-AC05-06OR23100). Los Alamos National Laboratory is operated by Los Alamos National Security, Limited Liability Corporation, for the National Nuclear Security Administration of U.S. Department of Energy (contract DE-AC52-06NA25396).

Keywords

Bromide
Organometallic
Trivalent and tetravalent uranium

Access to Document

10.3390/inorganics4010001

Fingerprint

Dive into the research topics of 'Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et)'. Together they form a unique fingerprint.

Cite this

Lichtscheidl, A. G., Pagano, J. K., Scott, B. L., Nelson, A. T., & Kiplinger, J. L. (2016). Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et). Inorganics, 4(1), Article 17. https://doi.org/10.3390/inorganics4010001

@article{480ecaec11554e6084662d99b3711e30,

title = "Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)",

abstract = "The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) withMe3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) {"}ate{"} species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.",

keywords = "Bromide, Organometallic, Trivalent and tetravalent uranium",

author = "Lichtscheidl, \{Alejandro G.\} and Pagano, \{Justin K.\} and Scott, \{Brian L.\} and Nelson, \{Andrew T.\} and Kiplinger, \{Jaqueline L.\}",

note = "Publisher Copyright: {\textcopyright} 2016 by the authors.",

year = "2016",

month = mar,

day = "1",

doi = "10.3390/inorganics4010001",

language = "English",

volume = "4",

journal = "Inorganics",

issn = "2304-6740",

publisher = "MDPI",

number = "1",

}

Lichtscheidl, AG, Pagano, JK, Scott, BL, Nelson, AT & Kiplinger, JL 2016, 'Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et)', Inorganics, vol. 4, no. 1, 17. https://doi.org/10.3390/inorganics4010001

Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et). / Lichtscheidl, Alejandro G.; Pagano, Justin K.; Scott, Brian L. et al.
In: Inorganics, Vol. 4, No. 1, 17, 01.03.2016.

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

TY - JOUR

T1 - Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes

T2 - (C5Me4R)2UBr2, (C5Me4R)2U(O-2,6-iPr2C6H3)(Br), and [K(THF)][(C5Me4R)2UBr2] (R = Me, Et)

AU - Lichtscheidl, Alejandro G.

AU - Pagano, Justin K.

AU - Scott, Brian L.

AU - Nelson, Andrew T.

AU - Kiplinger, Jaqueline L.

PY - 2016/3/1

Y1 - 2016/3/1

N2 - The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) withMe3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) "ate" species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.

AB - The organometallic uranium species (C5Me4R)2UBr2 (R = Me, Et) were obtained by treating their chloride analogues (C5Me4R)2UCl2 (R = Me, Et) with Me3SiBr. Treatment of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with K(O-2,6-iPr2C6H3) afforded the halide aryloxide mixed-ligand complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(X) (R = Me, Et; X = Cl, Br). Complexes (C5Me4R)2U(O-2,6-iPr2C6H3)(Br) (R = Me, Et) can also be synthesized by treating (C5Me4R)2U(O-2,6-iPr2C6H3)(Cl) (R = Me, Et) withMe3SiBr, respectively. Reduction of (C5Me4R)2UCl2 and (C5Me4R)2UBr2 (R = Me, Et) with KC8 led to isolation of uranium(III) "ate" species [K(THF)][(C5Me5)2UX2] (X = Cl, Br) and [K(THF)0.5][(C5Me4Et)2UX2] (X = Cl, Br), which can be converted to the neutral complexes (C5Me4R)2U[N(SiMe3)2] (R = Me, Et). Analyses by nuclear magnetic resonance spectroscopy, X-ray crystallography, and elemental analysis are also presented.

KW - Bromide

KW - Organometallic

KW - Trivalent and tetravalent uranium

UR - https://www.scopus.com/pages/publications/85061009915

U2 - 10.3390/inorganics4010001

DO - 10.3390/inorganics4010001

M3 - Article

AN - SCOPUS:85061009915

SN - 2304-6740

VL - 4

JO - Inorganics

JF - Inorganics

IS - 1

M1 - 17

ER -

Lichtscheidl AG, Pagano JK, Scott BL, Nelson AT, Kiplinger JL. Expanding the chemistry of actinide metallocene bromides. synthesis, properties and molecular structures of the tetravalent and trivalent uranium bromide complexes: (C₅Me₄R)₂UBr2, (C₅Me₄R)₂U(O-2,6-ⁱPr₂C₆H₃)(Br), and [K(THF)][(C₅Me₄R)₂UBr₂] (R = Me, Et). Inorganics. 2016 Mar 1;4(1):17. doi: 10.3390/inorganics4010001