X-ray Crystal Structure of Thorium Tetrahydroborate, Th(BH4)4, and Computational Studies of An(BH4)4(An = Th, U)

Andrew C. Dunbar; Joseph C. Wright; Daniel J. Grant; Gregory S. Girolami

doi:10.1021/acs.inorgchem.1c01710

X-ray Crystal Structure of Thorium Tetrahydroborate, Th(BH₄)₄, and Computational Studies of An(BH₄)₄(An = Th, U)

Andrew C. Dunbar, Joseph C. Wright, Daniel J. Grant, Gregory S. Girolami

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

Abstract

The crystal structure of Th(BH4)4 is described. Two of the four BH4- ions are terminal and tridentate (κ3), whereas the other two bridge between neighboring ThIV centers in a κ2,κ2 (i.e., bis-bidentate) fashion. Thus, each thorium center is bound to six BH4- groups by 14 Th-H bonds. The six boron atoms describe a distorted octahedron in which the κ3-BH4- ions are mutually cis; the 14 ligating hydrogen atoms define a highly distorted bicapped hexagonal antiprism. The thorium centers are linked into a polymer consisting of interconnected helical chains wound about 4-fold screw axes. The structures of An(BH4)4 (An = Th, U) were also investigated by DFT. The geometries of [An(BH4)6]2-, [An3(BH4)16]4-, and [An5(BH4)26]6- fragments of the polymeric structures were optimized at the B3LYP and/or PBE levels. Most calculated geometries are 14-coordinate and agree with the experimental structures, but isolated [Th(BH4)6]2- units are predicted to feature 16-coordinate ThIV centers.

Original language	English (US)
Pages (from-to)	12489-12497
Number of pages	9
Journal	Inorganic Chemistry
Volume	60
Issue number	16
DOIs	https://doi.org/10.1021/acs.inorgchem.1c01710
State	Published - Aug 16 2021

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.1c01710

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@article{79b34659fed44d2b9d5f545a3753c096,

title = "X-ray Crystal Structure of Thorium Tetrahydroborate, Th(BH4)4, and Computational Studies of An(BH4)4(An = Th, U)",

abstract = "The crystal structure of Th(BH4)4 is described. Two of the four BH4- ions are terminal and tridentate (κ3), whereas the other two bridge between neighboring ThIV centers in a κ2,κ2 (i.e., bis-bidentate) fashion. Thus, each thorium center is bound to six BH4- groups by 14 Th-H bonds. The six boron atoms describe a distorted octahedron in which the κ3-BH4- ions are mutually cis; the 14 ligating hydrogen atoms define a highly distorted bicapped hexagonal antiprism. The thorium centers are linked into a polymer consisting of interconnected helical chains wound about 4-fold screw axes. The structures of An(BH4)4 (An = Th, U) were also investigated by DFT. The geometries of [An(BH4)6]2-, [An3(BH4)16]4-, and [An5(BH4)26]6- fragments of the polymeric structures were optimized at the B3LYP and/or PBE levels. Most calculated geometries are 14-coordinate and agree with the experimental structures, but isolated [Th(BH4)6]2- units are predicted to feature 16-coordinate ThIV centers.",

author = "Dunbar, {Andrew C.} and Wright, {Joseph C.} and Grant, {Daniel J.} and Girolami, {Gregory S.}",

note = "Funding Information: G.S.G. acknowledges funding from the National Science Foundation (CHE-19-54745), which supported the work of A.C.D., and the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Separation Science Program, under Award DE-SC0019021, which supported the work of J.C.W. We thank Dr. Danielle Gray and Amy Fuller of the George L. Clark X-ray Facility at the University of Illinois at Urbana–Champaign for collecting the X-ray diffraction data. We also thank Prof. Laura Gagliardi, formerly of the University of Minnesota and now at the University of Chicago, for her valuable advice and assistance. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = aug,

day = "16",

doi = "10.1021/acs.inorgchem.1c01710",

language = "English (US)",

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T1 - X-ray Crystal Structure of Thorium Tetrahydroborate, Th(BH4)4, and Computational Studies of An(BH4)4(An = Th, U)

AU - Dunbar, Andrew C.

AU - Wright, Joseph C.

AU - Grant, Daniel J.

AU - Girolami, Gregory S.

N1 - Funding Information: G.S.G. acknowledges funding from the National Science Foundation (CHE-19-54745), which supported the work of A.C.D., and the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Separation Science Program, under Award DE-SC0019021, which supported the work of J.C.W. We thank Dr. Danielle Gray and Amy Fuller of the George L. Clark X-ray Facility at the University of Illinois at Urbana–Champaign for collecting the X-ray diffraction data. We also thank Prof. Laura Gagliardi, formerly of the University of Minnesota and now at the University of Chicago, for her valuable advice and assistance. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/8/16

Y1 - 2021/8/16

N2 - The crystal structure of Th(BH4)4 is described. Two of the four BH4- ions are terminal and tridentate (κ3), whereas the other two bridge between neighboring ThIV centers in a κ2,κ2 (i.e., bis-bidentate) fashion. Thus, each thorium center is bound to six BH4- groups by 14 Th-H bonds. The six boron atoms describe a distorted octahedron in which the κ3-BH4- ions are mutually cis; the 14 ligating hydrogen atoms define a highly distorted bicapped hexagonal antiprism. The thorium centers are linked into a polymer consisting of interconnected helical chains wound about 4-fold screw axes. The structures of An(BH4)4 (An = Th, U) were also investigated by DFT. The geometries of [An(BH4)6]2-, [An3(BH4)16]4-, and [An5(BH4)26]6- fragments of the polymeric structures were optimized at the B3LYP and/or PBE levels. Most calculated geometries are 14-coordinate and agree with the experimental structures, but isolated [Th(BH4)6]2- units are predicted to feature 16-coordinate ThIV centers.

AB - The crystal structure of Th(BH4)4 is described. Two of the four BH4- ions are terminal and tridentate (κ3), whereas the other two bridge between neighboring ThIV centers in a κ2,κ2 (i.e., bis-bidentate) fashion. Thus, each thorium center is bound to six BH4- groups by 14 Th-H bonds. The six boron atoms describe a distorted octahedron in which the κ3-BH4- ions are mutually cis; the 14 ligating hydrogen atoms define a highly distorted bicapped hexagonal antiprism. The thorium centers are linked into a polymer consisting of interconnected helical chains wound about 4-fold screw axes. The structures of An(BH4)4 (An = Th, U) were also investigated by DFT. The geometries of [An(BH4)6]2-, [An3(BH4)16]4-, and [An5(BH4)26]6- fragments of the polymeric structures were optimized at the B3LYP and/or PBE levels. Most calculated geometries are 14-coordinate and agree with the experimental structures, but isolated [Th(BH4)6]2- units are predicted to feature 16-coordinate ThIV centers.

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U2 - 10.1021/acs.inorgchem.1c01710

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