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

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

doi:10.1021/acs.inorgchem.1c01710

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

Journal Article · 04 August 2021 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.1c01710 · OSTI ID:1903739

Dunbar, Andrew C. ^[1]; Wright, Joseph C. ^[2]; Grant, Daniel J. ^[3];

^[2]

Univ. of Illinois at Urbana-Champaign, IL (United States); University of Illinois at Urbana-Champaign
Univ. of Illinois at Urbana-Champaign, IL (United States)
Univ. of Minnesota, Minneapolis, MN (United States)

Here 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 Th^IV 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 Th^IV centers.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: University of Illinois at Urbana-Champaign, Urbana, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0019021; SC0019426

OSTI ID:: 1903739

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 16 Vol. 60; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (54)

Synthesis and Properties of a Fifteen-Coordinate Complex: The Thorium Aminodiboranate [Th(H3BNMe2BH3)4] Daly, Scott R.; Piccoli, Paula M. B.; Schultz, Arthur J. Angewandte Chemie International Edition, Vol. 49, Issue 19 https://doi.org/10.1002/anie.200905797	journal	March 2010
Boron-based hydrides for chemical hydrogen storage: Boron-based hydrolytic and thermolytic hydrides Moussa, Georges; Moury, Romain; Demirci, Umit B. International Journal of Energy Research, Vol. 37, Issue 8 https://doi.org/10.1002/er.3027	journal	March 2013
Metallboranate und Boranatometallate. IV. Boranatokomplexe M(BH4)4+nn? des Zirkoniums, Hafniums und Thoriums Ehemann, Manfred; N�th, Heinrich Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 386, Issue 1 https://doi.org/10.1002/zaac.19713860110	journal	December 1971
On the indenyl compounds of actinide elements Part IV: Preparation and properties of the trisindenyl thorium tetrahydroborate Goffart, J.; Michel, G.; Gilbert, B. P. Inorganic and Nuclear Chemistry Letters, Vol. 14, Issue 11 https://doi.org/10.1016/0020-1650(78)80004-X	journal	January 1978
Uranium(IV) borohydride: A new crystalline form Charpin, Pierrette; Marquet-Ellis, Hubert; Folcher, Gérard Journal of Inorganic and Nuclear Chemistry, Vol. 41, Issue 8 https://doi.org/10.1016/0022-1902(79)80472-8	journal	January 1979
The chemical vapor deposition of TiB2 on graphite Pierson, H. O.; Randich, E.; Mattox, D. M. Journal of the Less Common Metals, Vol. 67, Issue 2 https://doi.org/10.1016/0022-5088(79)90016-X	journal	October 1979
Titanium diboride-coated boron fibre for aluminium matrix composites Bouix, J.; Vincent, H.; Boubehira, M. Journal of the Less Common Metals, Vol. 117, Issue 1-2 https://doi.org/10.1016/0022-5088(86)90014-7	journal	March 1986
Titanium diboride coatings and their interaction with the substrates Pierson, H. O.; Randich, E. Thin Solid Films, Vol. 54, Issue 1 https://doi.org/10.1016/0040-6090(78)90282-1	journal	October 1978
Metal (boro-) hydrides for high energy density storage and relevant emerging technologies Bannenberg, L. J.; Heere, M.; Benzidi, H. International Journal of Hydrogen Energy, Vol. 45, Issue 58 https://doi.org/10.1016/j.ijhydene.2020.08.119	journal	November 2020
Ca(BH4)2 as a simple tool for the preparation of thorium and uranium metallocene borohydride complexes: First synthesis and crystal structure of (C5Me5)2Th(η3-H3BH)2 Erickson, Karla A.; Scott, Brian L.; Kiplinger, Jaqueline L. Inorganic Chemistry Communications, Vol. 77 https://doi.org/10.1016/j.inoche.2017.01.019	journal	March 2017
Crystalline texture in hafnium diboride thin films grown by chemical vapor deposition Yang, Yu; Jayaraman, Sreenivas; Kim, Do Young Journal of Crystal Growth, Vol. 294, Issue 2 https://doi.org/10.1016/j.jcrysgro.2006.05.035	journal	September 2006
Synthesis and characterization of phosphine adducts of thorium borohydride, Th(BH4)4 Dunbar, Andrew C.; Gozum, John E.; Girolami, Gregory S. Journal of Organometallic Chemistry, Vol. 695, Issue 25-26 https://doi.org/10.1016/j.jorganchem.2010.09.033	journal	December 2010
Development of metal borohydrides for hydrogen storage Nakamori, Y.; Li, H. -W.; Matsuo, M. Journal of Physics and Chemistry of Solids, Vol. 69, Issue 9 https://doi.org/10.1016/j.jpcs.2008.04.017	journal	September 2008
Direct borohydride fuel cells de Leon, C. Ponce; Walsh, F. C.; Pletcher, D. Journal of Power Sources, Vol. 155, Issue 2 https://doi.org/10.1016/j.jpowsour.2006.01.011	journal	April 2006
Synthesis and Characterization of Protactinium(IV), Neptunium(IV), and Plutonium (IV) Borohydrides Banks, Rodney H.; Edelstein, Norman M. Lanthanide and Actinide Chemistry and Spectroscopy https://doi.org/10.1021/bk-1980-0131.ch016	book	September 1980
CVD Growth Kinetics of HfB ₂ Thin Films from the Single-Source Precursor Hf(BH ₄ ) ₄ Yang, Yu; Jayaraman, Sreenivas; Kim, Do Young Chemistry of Materials, Vol. 18, Issue 21 https://doi.org/10.1021/cm0605421	journal	September 2006
Titanium Diboride Thin Films by Low-Temperature Chemical Vapor Deposition from the Single Source Precursor Ti(BH ₄ ) ₃ (1,2-dimethoxyethane) Kumar, Navneet; Yang, Yu; Noh, Wontae Chemistry of Materials, Vol. 19, Issue 15 https://doi.org/10.1021/cm070277z	journal	June 2007
Covalent transition metal, lanthanide, and actinide tetrahydroborate complexes Marks, Tobin J.; Kolb, John R. Chemical Reviews, Vol. 77, Issue 2 https://doi.org/10.1021/cr60306a004	journal	April 1977
Synthesis, Structure, and Reactions of Hydride, Borohydride, and Aluminohydride Compounds of the f-Elements Ephritikhine, Michel Chemical Reviews, Vol. 97, Issue 6 https://doi.org/10.1021/cr960366n	journal	October 1997
Syntheses and crystal structures of the tetrakis(methyltrihydroborato) compounds of zirconium(IV), thorium(IV), uranium(IV), and neptunium(IV) Shinomoto, Ron; Gamp, Eduard; Edelstein, Norman M. Inorganic Chemistry, Vol. 22, Issue 17 https://doi.org/10.1021/ic00159a003	journal	August 1983
Bridging of thorium by hydrogen atoms of methyltrihydroborate groups. Crystal structures of bis[tetrakis(methyltrihydroborato)thorium(IV)] etherate and bis[tetrakis(methyltrihydroborato)thorium(IV) tetrahydrofuranate] Shinomoto, Ron; Brennan, John G.; Edelstein, Norman M. Inorganic Chemistry, Vol. 24, Issue 19 https://doi.org/10.1021/ic00213a005	journal	September 1985
Observation of the Inverse Trans Influence (ITI) in a Uranium(V) Imide Coordination Complex: An Experimental Study and Theoretical Evaluation Lam, Oanh P.; Franke, Sebastian M.; Nakai, Hidetaka Inorganic Chemistry, Vol. 51, Issue 11 https://doi.org/10.1021/ic300273d	journal	May 2012
The Inverse Trans Influence in a Family of Pentavalent Uranium Complexes Lewis, Andrew J.; Mullane, Kimberly C.; Nakamaru-Ogiso, Eiko Inorganic Chemistry, Vol. 53, Issue 13 https://doi.org/10.1021/ic500833s	journal	June 2014
Structure and dynamics in metal tetrahydroborates. II. Vibrational spectra and structures of some transition metal and actinide tetrahydroborates Marks, Tobin J.; Kennelly, William J.; Kolb, John R. Inorganic Chemistry, Vol. 11, Issue 10 https://doi.org/10.1021/ic50116a051	journal	October 1972
14-Coordinate uranium(IV). Structure of uranium borohydride by single-crystal neutron diffraction Bernstein, E. R.; Hamilton, Walter C.; Keiderling, T. A. Inorganic Chemistry, Vol. 11, Issue 12 https://doi.org/10.1021/ic50118a027	journal	December 1972
Chloro-, methyl-, and (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) and uranium(IV). Crystal structure of (tetrahydroborato)tris((hexamethyldisilyl)amido)thorium(IV) Turner, Howard W.; Andersen, Richard A.; Zalkin, Allan Inorganic Chemistry, Vol. 18, Issue 5 https://doi.org/10.1021/ic50195a008	journal	May 1979
Volatile Magnesium Octahydrotriborate Complexes as Potential CVD Precursors to MgB ₂ . Synthesis and Characterization of Mg(B ₃ H ₈ ) ₂ and Its Etherates Kim, Do Young; Yang, Yu; Abelson, John R. Inorganic Chemistry, Vol. 46, Issue 22 https://doi.org/10.1021/ic701037t	journal	October 2007
Covalent Bonding and the Trans Influence in Lanthanide Compounds Krogh-Jespersen, Karsten; Romanelli, Michael D.; Melman, Jonathan H. Inorganic Chemistry, Vol. 49, Issue 2 https://doi.org/10.1021/ic901571m	journal	January 2010
Titanium, zirconium, and hafnium tetrahydroborates as "tailored" CVD precursors for metal diboride thin films Jensen, James A.; Gozum, John E.; Pollina, Deborah M. Journal of the American Chemical Society, Vol. 110, Issue 5 https://doi.org/10.1021/ja00213a058	journal	March 1988
Preparation and properties of the actinide borohydrides: protactinium(IV), neptunium(IV), and plutonium(IV) borohydrides Banks, R. H.; Edelstein, N. M.; Rietz, R. R. Journal of the American Chemical Society, Vol. 100, Issue 6 https://doi.org/10.1021/ja00474a067	journal	March 1978
Volatility and molecular structure of neptunium(IV) borohydride Banks, Rodney H.; Edelstein, Norman M.; Spencer, Brock Journal of the American Chemical Society, Vol. 102, Issue 2 https://doi.org/10.1021/ja00522a029	journal	January 1980
Structure of uranium borohydride by single-crystal x-ray diffraction Bernstein, E. R.; Keiderling, T. A.; Lippard, S. J. Journal of the American Chemical Society, Vol. 94, Issue 7 https://doi.org/10.1021/ja00762a082	journal	April 1972
Uranium(IV) Borohydride ¹ Schlesinger, H. I.; Brown, Herbert C. Journal of the American Chemical Society, Vol. 75, Issue 1 https://doi.org/10.1021/ja01097a058	journal	January 1953
The Preparation and Properties of the Group IV-B Metal Borohydrides Hoekstra, H. R.; Katz, J. J. Journal of the American Chemical Society, Vol. 71, Issue 7 https://doi.org/10.1021/ja01175a073	journal	July 1949
Lanthanide N , N -Dimethylaminodiboranates: Highly Volatile Precursors for the Deposition of Lanthanide-Containing Thin Films Daly, Scott R.; Kim, Do Young; Yang, Yu Journal of the American Chemical Society, Vol. 132, Issue 7 https://doi.org/10.1021/ja9098005	journal	February 2010
Volatilities of Actinide and Lanthanide N , N -Dimethylaminodiboranate Chemical Vapor Deposition Precursors: A DFT Study Vlaisavljevich, Bess; Miró, Pere; Koballa, Drew The Journal of Physical Chemistry C, Vol. 116, Issue 44 https://doi.org/10.1021/jp305691y	journal	October 2012
Direct Writing of Sub-5 nm Hafnium Diboride Metallic Nanostructures Ye, Wei; Peña Martin, Pamela A.; Kumar, Navneet ACS Nano, Vol. 4, Issue 11 https://doi.org/10.1021/nn1018522	journal	October 2010
Bis(permethylindenyl) Complexes of Thorium: Synthesis, Structure, and Reactivity Trnka, Tina M.; Bonanno, Jeffrey B.; Bridgewater, Brian M. Organometallics, Vol. 20, Issue 15 https://doi.org/10.1021/om010233e	journal	July 2001
The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes Gregson, Matthew; Lu, Erli; Mills, David P. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14137	journal	February 2017
Field-directed sputter sharpening for tailored probe materials and atomic-scale lithography Schmucker, S. W.; Kumar, N.; Abelson, J. R. Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1907	journal	January 2012
Arene-ligated heteroleptic terphenolate complexes of thorium McKinven, Jamie; Nichol, Gary S.; Arnold, Polly L. Dalton Trans., Vol. 43, Issue 46 https://doi.org/10.1039/C4DT02995J	journal	January 2014
Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex Settineri, Nicholas S.; Arnold, John Chemical Science, Vol. 9, Issue 10 https://doi.org/10.1039/C7SC05328B	journal	January 2018
New theoretical insights into high-coordination-number complexes in actinides-centered borane Hu, Shu-Xian; Zhang, Peng; Zou, Wenli Nanoscale, Vol. 12, Issue 28 https://doi.org/10.1039/D0NR01955K	journal	January 2020
Remote-plasma chemical vapor deposition of conformal ZrB2 films at low temperature: A promising diffusion barrier for ultralarge scale integrated electronics Sung, Junghwan; Goedde, Dean M.; Girolami, Gregory S. Journal of Applied Physics, Vol. 91, Issue 6 https://doi.org/10.1063/1.1436296	journal	March 2002
Atomic Radii in Crystals Slater, J. C. The Journal of Chemical Physics, Vol. 41, Issue 10 https://doi.org/10.1063/1.1725697	journal	November 1964
Structure of the second crystalline form of uranium(IV) tetrahydroborate Charpin, P.; Nierlich, M.; Vigner, D. Acta Crystallographica Section C Crystal Structure Communications, Vol. 43, Issue 8 https://doi.org/10.1107/S0108270187091431	journal	August 1987
Crystal chemical studies of the 5 f -series of elements. XIX. The crystal structure of the higher thorium hydride, Th ₄ H ₁₅ Zachariasen, W. H. Acta Crystallographica, Vol. 6, Issue 5 https://doi.org/10.1107/S0365110X53001095	journal	May 1953
Chromium diboride thin films by low temperature chemical vapor deposition Jayaraman, Sreenivas; Klein, Emily J.; Yang, Yu Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 23, Issue 4 https://doi.org/10.1116/1.1927534	journal	July 2005
Hafnium diboride thin films by chemical vapor deposition from a single source precursor Jayaraman, Sreenivas; Yang, Yu; Kim, Do Young Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 23, Issue 6 https://doi.org/10.1116/1.2049307	journal	November 2005
In situ spectroscopic ellipsometry analyses of hafnium diboride thin films deposited by single-source chemical vapor deposition Yang, Yu; Jayaraman, Sreenivas; Sperling, Brent Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 25, Issue 1 https://doi.org/10.1116/1.2409939	journal	January 2007
Conformal MgO film grown at high rate at low temperature by forward-directed chemical vapor deposition Talukdar, Tushar K.; Liu, Sumeng; Zhang, Zhejun Journal of Vacuum Science & Technology A, Vol. 36, Issue 5 https://doi.org/10.1116/1.5040855	journal	September 2018
Chemical Vapor Deposition of Erosion‐Resistant TiB2 Coatings Caputo, A. J.; Lackey, W. J.; Wright, I. G. Journal of The Electrochemical Society, Vol. 132, Issue 9 https://doi.org/10.1149/1.2114334	journal	September 1985
Recent Progress in Metal Borohydrides for Hydrogen Storage Li, Hai-Wen; Yan, Yigang; Orimo, Shin-ichi Energies, Vol. 4, Issue 1 https://doi.org/10.3390/en4010185	journal	January 2011
Metal Borohydrides beyond Groups I and II: A Review Suárez-Alcántara, Karina; Tena García, Juan Rogelio Materials, Vol. 14, Issue 10 https://doi.org/10.3390/ma14102561	journal	May 2021

Similar Records

Oligomerization of metal-oxygen bonds in thorium alkoxide chemistry: X-ray crystal structures of Th{sub 4}(O-i-Pr){sub 16}(py){sub 2} and Th{sub 2}(OCHEt{sub 2}){sub 8}(py){sub 2}

Journal Article · 1994 · Inorganic Chemistry · OSTI ID:457878

Barnhart, D M; Clark, D L; Gordon, J C

Preparation and crystal structure of uranium(IV) borohydride-bis(tetrahydrofuran), U(BH/sub 4/)/sub 4/. 2OC/sub 4/H/sub 8/

Journal Article · 1978 · Inorg. Chem.; (United States) · OSTI ID:5121390

Rietz, R R; Edelstein, N M; Ruben, H W; +2 more

Metrical characterization of tridentate tetrahydroborate ligation to a transition-metal ion. Structure and bonding in Hf(BH/sub 4/)/sub 4/ by single-crystal neutron diffraction

Journal Article · 1983 · Inorg. Chem.; (United States) · OSTI ID:5438666

Broach, R W; Chuang, I S; Marks, T J; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical structure
crystal structure
group theory
ligands
thorium

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

Citation Formats

References (54)

Linked Research (1)

Similar Records

Related Subjects

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