Synthesis of bulky hydride ligands: m-terphenylborohydride complexes with trivalent uranium and neodymium

Zacher, III, Peter A.; Unruh, Daniel K.; Daly, Scott R.

doi:10.1039/D5DT01076D

Synthesis of bulky hydride ligands: m-terphenylborohydride complexes with trivalent uranium and neodymium

Journal Article · Wed May 28 00:00:00 EDT 2025 · Dalton Transactions

DOI:https://doi.org/10.1039/D5DT01076D· OSTI ID:2569218

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University of Iowa, Iowa City, IA (United States)

Here we describe the first coordination complexes containing a bulky m-terphenyltrihydroborate ligand. Treating [UI₃(thf)₄] and NdCl₃ with three equiv. of Li(H₃BAr^tBu4)(Et₂O) (where Ar^tBu4 = 2,6-(3,5-^tBu₂C₆H₃)₂C₆H₃) yielded [M(H₃BAr^tBu4)₃(thf)₂] (M = U and Nd). [U(H₃BAr^tBu4)₃(dme)₂] is also described, and structural comparisons reveal the influence of the Lewis base on H₃BAr^tBu4 positioning.

View Accepted Manuscript (DOE)

Research Organization:: Georgia Tech Research Corporation, Atlanta, GA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)

Grant/Contract Number:: NA0004151

OSTI ID:: 2569218

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 23 Vol. 54; ISSN 1477-9226; ISSN 1477-9234

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Ligand Design in Modern Lanthanide Chemistry Mills, David P.; Liddle, Stephen T. Ligand Design in Metal Chemistry: Reactivity and Catalysis https://doi.org/10.1002/9781118839621.ch12	book	January 2016
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
f‐Element Half‐Sandwich Complexes: A Tetrasilylcyclobutadienyl–Uranium(IV)–Tris(tetrahydroborate) Anion Pianostool Complex Boronski, Josef T.; Doyle, Laurence R.; Seed, John A. Angewandte Chemie International Edition, Vol. 59, Issue 1 https://doi.org/10.1002/anie.201913640	journal	December 2019
Quantifying the Influence of Covalent Metal‐Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes Fetrow, Taylor V.; Zgrabik, Joshua; Bhowmick, Rina Angewandte Chemie International Edition, Vol. 61, Issue 45 https://doi.org/10.1002/anie.202211145	journal	October 2022
Transition Metal Complexes Stabilized by Bulky Terphenyl Ligands: Application to Metal–Metal Bonded Compounds Ni, Chengbao; Power, Philip P. Metal-Metal Bonding https://doi.org/10.1007/978-3-642-05243-9_3	book	January 2010
Unusual structures of main group organometallic compounds containing m-terphenyl ligands Clyburne, Jason A. C.; McMullen, Nichole Coordination Chemistry Reviews, Vol. 210, Issue 1, p. 73-99 https://doi.org/10.1016/S0010-8545(00)00317-9	journal	December 2000
Element Derivatives of Sterically Encumbering Terphenyl Ligands Twamley, Brendan; Haubrich, Scott T.; Power, Philip P. Advances in Organometallic Chemistry https://doi.org/10.1016/S0065-3055(08)60619-X	book	January 1999
Convenient Syntheses of Trivalent Uranium Halide Starting Materials without Uranium Metal Fetrow, Taylor V.; Grabow, J. Peter; Leddy, Johna Inorganic Chemistry, Vol. 60, Issue 11 https://doi.org/10.1021/acs.inorgchem.1c00598	journal	May 2021
Pr(H₃BNMe₂BH₃)₃ and Pr(thd)₃ as Volatile Carriers for Actinium-225. Deposition of Actinium-Doped Praseodymium Boride Thin Films for Potential Use in Brachytherapy Daly, Scott R.; Bellott, Brian J.; McAlister, Daniel R. Inorganic Chemistry, Vol. 61, Issue 19 https://doi.org/10.1021/acs.inorgchem.2c00442	journal	May 2022
The Influence of Phosphorus Substituents on the Structures and Solution Speciation of Trivalent Uranium and Lanthanide Phosphinodiboranates Zgrabik, Joshua C.; Bhowmick, Rina; Eckstrom, Francesca D. Inorganic Chemistry, Vol. 63, Issue 21, p. 9451-9463 https://doi.org/10.1021/acs.inorgchem.3c02773	journal	November 2023
Uranium(III) and Uranium(IV) meta-Terphenylthiolate Complexes Réant, Benjamin L. L.; Seed, John A.; Whitehead, George F. S. Inorganic Chemistry, Vol. 64, Issue 7, p. 3161-3177 https://doi.org/10.1021/acs.inorgchem.4c03085	journal	February 2025
Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates Fetrow, Taylor V.; Bhowmick, Rina; Achazi, Andreas J. Inorganic Chemistry, Vol. 59, Issue 1 https://doi.org/10.1021/acs.inorgchem.9b01628	journal	August 2019
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
A Convenient Entry into Trivalent Actinide Chemistry: Synthesis and Characterization of AnI3(THF)4 and An[N(SiMe3)2]3 (An = U, Np, Pu) Avens, Larry R.; Bott, Simon G.; Clark, David L. Inorganic Chemistry, Vol. 33, Issue 10 https://doi.org/10.1021/ic00088a030	journal	May 1994
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
Synthesis, Characterization, and Structures of Uranium(III) N , N -Dimethylaminodiboranates Daly, Scott R.; Girolami, Gregory S. Inorganic Chemistry, Vol. 49, Issue 11 https://doi.org/10.1021/ic100290j	journal	June 2010
Multiple Bonding in Heavier Element Compounds Stabilized by Bulky Terphenyl Ligands Rivard, Eric; Power, Philip P. Inorganic Chemistry, Vol. 46, Issue 24 https://doi.org/10.1021/ic700813h	journal	November 2007
Lanthanide(III) and Actinide(III) Complexes [M(BH ₄ ) ₂ (THF) ₅ ][BPh ₄ ] and [M(BH ₄ ) ₂ (18-crown-6)][BPh ₄ ] (M = Nd, Ce, U): Synthesis, Crystal Structure, and Density Functional Theory Investigation of the Covalent Contribution to Metal-Borohydride Bonding Arliguie, Thérèse; Belkhiri, Lotfi; Bouaoud, Salah-Eddine Inorganic Chemistry, Vol. 48, Issue 1 https://doi.org/10.1021/ic801685v	journal	January 2009
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
New Developments in the Chemistry of Diborane and the Borohydrides. I. General Summary ¹ Schlesinger, H. I.; Brown, Herbert C.; Abraham, B. Journal of the American Chemical Society, Vol. 75, Issue 1 https://doi.org/10.1021/ja01097a049	journal	January 1953
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 Methyl Derivatives of Uranium(IV) Borohydride ¹ Schlesinger, H. I.; Brown, Herbert C.; Horvitz, L. Journal of the American Chemical Society, Vol. 75, Issue 1 https://doi.org/10.1021/ja01097a059	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
New Chemistry from an Old Reagent: Mono- and Dinuclear Macrocyclic Uranium(III) Complexes from [U(BH ₄ ) ₃ (THF) ₂ ] Arnold, Polly L.; Stevens, Charlotte J.; Farnaby, Joy H. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja504835a	journal	July 2014
Structural and Theoretical Assessment of Covalency in a Pu(III) Borohydride Complex Zgrabik, Joshua C.; Lussier, Daniel J.; Bhowmick, Rina Journal of the American Chemical Society, Vol. 146, Issue 38 https://doi.org/10.1021/jacs.4c09888	journal	September 2024
A Homoleptic Uranium(III) Tris(aryl) Complex Boreen, Michael A.; Parker, Bernard F.; Lohrey, Trevor D. Journal of the American Chemical Society, Vol. 138, Issue 49 https://doi.org/10.1021/jacs.6b11182	journal	December 2016
Synthesis and Characterization of a Neutral U(II) Arene Sandwich Complex Billow, Brennan S.; Livesay, Brooke N.; Mokhtarzadeh, Charles C. Journal of the American Chemical Society, Vol. 140, Issue 50 https://doi.org/10.1021/jacs.8b10888	journal	November 2018
Addition compounds of alkali-metal hydrides. 25. Rapid reaction of boronic esters and acids with lithium aluminum hydride. A novel and quantitative synthesis of lithium monoorganylborohydrides Singaram, Bakthan; Cole, Thomas E.; Brown, Herbert C. Organometallics, Vol. 3, Issue 5 https://doi.org/10.1021/om00083a022	journal	May 1984
Unsymmetrical 9-Borafluorenes via Low-Temperature C−H Activation of m-Terphenylboranes Wehmschulte, Rudolf J.; Diaz, Armando A.; Khan, Masood A. Organometallics, Vol. 22, Issue 1, p. 83-92 https://doi.org/10.1021/om020611v	journal	November 2002
Cyclometalation and Solvent Deoxygenation during Reduction of a Homoleptic Th(OAr) ₄ Complex: Serendipitous Formation of a Terminally Bonded Th−OH Function Korobkov, Ilia; Arunachalampillai, Athimoolan; Gambarotta, Sandro Organometallics, Vol. 23, Issue 26 https://doi.org/10.1021/om049369d	journal	November 2004
Reactions of neodymium(ii), dysprosium(ii), and thulium(ii) diiodides with cyclopentadiene. Molecular structures of complexes CpTmI₂(THF)₃ and [NdI₂(THF)₅]⁺[NdI₄(THF)₂]^– Khoroshen'kov, G. V.; Fagin, A. A.; Bochkarev, M. N. Russian Chemical Bulletin, Vol. 52, Issue 8, p. 1715-1719 https://doi.org/10.1023/A:1026132017155	journal	January 2003
Uranium–hydrogen interactions: synthesis and crystal structures of tris(N,N-dimethylaminodiboranato)uranium(iii) Daly, Scott R.; Girolami, Gregory S. Chem. Commun., Vol. 46, Issue 3 https://doi.org/10.1039/B919490H	journal	January 2010
Extremely bulky amide ligands in main group chemistry Kays, Deborah L. Chemical Society Reviews, Vol. 45, Issue 4, p. 1004-1018 https://doi.org/10.1039/C5CS00513B	journal	January 2016
f-Block complexes of a m -terphenyl dithiocarboxylate ligand Boreen, Michael A.; Parker, Bernard F.; Hohloch, Stephan Dalton Transactions, Vol. 47, Issue 1 https://doi.org/10.1039/C7DT04073C	journal	January 2018
Homoleptic uranium and lanthanide phosphinodiboranates Blake, Anastasia V.; Fetrow, Taylor V.; Theiler, Zachary J. Chemical Communications, Vol. 54, Issue 44 https://doi.org/10.1039/C8CC02862A	journal	January 2018
Structural and electronic studies of substituted m-terphenyl lithium complexes Valentine, Andrew J.; Geer, Ana M.; Taylor, Laurence J. Dalton Transactions, Vol. 50, Issue 2, p. 722-728 https://doi.org/10.1039/D0DT03972A	journal	January 2021
Mechanochemical synthesis and structural analysis of trivalent lanthanide and uranium diphenylphosphinodiboranates Fetrow, Taylor V.; Daly, Scott R. Dalton Transactions, Vol. 50, Issue 33 https://doi.org/10.1039/D1DT01932E	journal	January 2021
Synthesis, structure, and spectroscopic properties of copper( II ) compounds containing nitrogen–sulphur donor ligands; the crystal and molecular structure of aqua[1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane]copper( II ) perchlorate Addison, Anthony W.; Rao, T. Nageswara; Reedijk, Jan J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9840001349	journal	January 1984
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976

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