Quantifying the Influence of Covalent Metal‐Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes

Fetrow, Taylor V.; Zgrabik, Joshua; Bhowmick, Rina; Eckstrom, Francesca D.; Crull, George; Vlaisavljevich, Bess; Daly, Scott R.

doi:10.1002/anie.202211145

Title: Quantifying the Influence of Covalent Metal‐Ligand Bonding on Differing Reactivity of Trivalent Uranium and Lanthanide Complexes

Journal Article · 11 October 2022 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202211145 · OSTI ID:1891931

^[1]; Zgrabik, Joshua ^[1]; Bhowmick, Rina ^[2]; Eckstrom, Francesca D. ^[1]; Crull, George ^[1];

^[2];

^[1]

Department of Chemistry The University of Iowa E331 Chemistry Building Iowa City IA 52242 USA
Department of Chemistry The University of South Dakota 414 East Clark Street Vermillion South Dakota 57069 USA

Abstract Qualitative differences in the reactivity of trivalent lanthanide and actinide complexes have long been attributed to differences in covalent metal‐ligand bonding, but there are few examples where thermodynamic aspects of this relationship have been quantified, especially with U ³⁺ and in the absence of competing variables. Here we report a series of dimeric phosphinodiboranate complexes with trivalent f ‐metals that show how shorter‐than‐expected U−B distances indicative of increased covalency give rise to measurable differences in solution deoligomerization reactivity when compared to isostructural complexes with similarly sized lanthanides. These results, which are in excellent agreement with supporting DFT and QTAIM calculations, afford rare experimental evidence concerning the measured effect of variations in metal‐ligand covalency on the reactivity of trivalent uranium and lanthanide complexes.

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Research Organization:: Univ. of Iowa, Iowa City, IA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019426

OSTI ID:: 1891931

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 45 Vol. 61; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (61)

Carbon Monoxide and Isocyanide Complexes of Trivalent Uranium Metallocenes del Mar Conejo, M.; Parry, Julian S.; Carmona, Ernesto Chemistry - A European Journal, Vol. 5, Issue 10 https://doi.org/10.1002/(SICI)1521-3765(19991001)5:10<3000::AID-CHEM3000>3.0.CO;2-Q	journal	October 1999
Coordination of Actinides and the Chemistry Behind Solvent Extraction Clark, Aurora E.; Yang, Ping; Shafer, Jenifer C. Experimental and Theoretical Approaches to Actinide Chemistry https://doi.org/10.1002/9781119115557.ch5	book	January 2018
Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS Lee, Kyounghoon; Blake, Anastasia V.; Donahue, Courtney M. Angewandte Chemie, Vol. 131, Issue 36 https://doi.org/10.1002/ange.201905635	journal	August 2019
Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules Goodwin, Conrad A. P.; Schlimgen, Anthony W.; Albrecht‐Schönzart, Thomas E. Angewandte Chemie, Vol. 133, Issue 17 https://doi.org/10.1002/ange.202017186	journal	March 2021
Quantifying the Interdependence of Metal–Ligand Covalency and Bond Distance Using Ligand K‐edge XAS Lee, Kyounghoon; Blake, Anastasia V.; Donahue, Courtney M. Angewandte Chemie International Edition, Vol. 58, Issue 36 https://doi.org/10.1002/anie.201905635	journal	August 2019
Structural and Spectroscopic Comparison of Soft‐Se vs. Hard‐O Donor Bonding in Trivalent Americium/Neodymium Molecules Goodwin, Conrad A. P.; Schlimgen, Anthony W.; Albrecht‐Schönzart, Thomas E. Angewandte Chemie International Edition, Vol. 60, Issue 17 https://doi.org/10.1002/anie.202017186	journal	March 2021
Lanthanide versus Actinide Reactivity in the Formation of Sterically Crowded [(C ₅ Me ₅ ) ₃ ML _n ] Nitrile and Isocyanide Complexes Evans, William J.; Mueller, Thomas J.; Ziller, Joseph W. Chemistry - A European Journal, Vol. 16, Issue 3 https://doi.org/10.1002/chem.200901990	journal	November 2009
Covalency in Actinide Compounds Pace, Kristen A.; Klepov, Vladislav V.; Berseneva, Anna A. Chemistry – A European Journal, Vol. 27, Issue 19 https://doi.org/10.1002/chem.202004632	journal	January 2021
Problems in the thermodynamics of the actinides in relation with the back-end of the nuclear fuel cycle Fuger, J. Journal of Nuclear Materials, Vol. 201 https://doi.org/10.1016/0022-3115(93)90154-Q	journal	May 1993
Aqueous complexation of trivalent lanthanide and actinide cations by N,N,N′,N′-tetrakis(2-pyridylmethyl)ethylenediamine Jensen, Mark P.; Morss, Lester R.; Beitz, James V. Journal of Alloys and Compounds, Vol. 303-304 https://doi.org/10.1016/S0925-8388(00)00620-4	journal	May 2000
Covalency in f-element bonds Choppin, Gregory R. Journal of Alloys and Compounds, Vol. 344, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)00305-5	journal	October 2002
Actinide speciation using X-ray absorption fine structure spectroscopy Denecke, M. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2005.09.004	journal	April 2006
Solution coordination chemistry of actinides: Thermodynamics, structure and reaction mechanisms Szabo, Z.; Toraishi, T.; Vallet, V. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2005.10.005	journal	April 2006
Recent advances in computational modeling and simulations on the An(III)/Ln(III) separation process Lan, Jian-Hui; Shi, Wei-Qun; Yuan, Li-Yong Coordination Chemistry Reviews, Vol. 256, Issue 13-14 https://doi.org/10.1016/j.ccr.2012.04.002	journal	July 2012
Covalency in f-element complexes Neidig, Michael L.; Clark, David L.; Martin, Richard L. Coordination Chemistry Reviews, Vol. 257, Issue 2 https://doi.org/10.1016/j.ccr.2012.04.029	journal	January 2013
Sulfur donating extractants for the separation of trivalent actinides and lanthanides Bessen, N. P.; Jackson, J. A.; Jensen, M. P. Coordination Chemistry Reviews, Vol. 421 https://doi.org/10.1016/j.ccr.2020.213446	journal	October 2020
Stronger Hydration of Eu(III) Impedes Its Competition against Am(III) in Binding with N-donor Extractants Xia, Miaoren; Yang, Xia; Chai, Zhifang Inorganic Chemistry, Vol. 59, Issue 9 https://doi.org/10.1021/acs.inorgchem.0c00374	journal	April 2020
Evidence for Participation of 4f and 5d Orbitals in Lanthanide Metal–Ligand Bonding and That Y(III) Has Less of This Complex-Stabilizing Ability. A Thermodynamic, Spectroscopic, and DFT Study of Their Complexation by the Nitrogen Donor Ligand TPEN Zanella, Brady S.; Jones, S. Bart; Lee, Hee-Seung Inorganic Chemistry, Vol. 61, Issue 11 https://doi.org/10.1021/acs.inorgchem.1c03443	journal	March 2022
Metal Bonding with 3d and 6d Orbitals: An EPR and ENDOR Spectroscopic Investigation of Ti ³⁺ –Al and Th ³⁺ –Al Heterobimetallic Complexes Rao, Guodong; Altman, Alison B.; Brown, Alexandra C. Inorganic Chemistry, Vol. 58, Issue 12 https://doi.org/10.1021/acs.inorgchem.9b00720	journal	June 2019
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
“Sweeping” Ortho Substituents Drive Desolvation and Overwhelm Electronic Effects in Nd ³⁺ Chelation: A Case of Three Aryldithiophosphinates Pu, Ning; Su, Jing; Xu, Lei Inorganic Chemistry, Vol. 59, Issue 1 https://doi.org/10.1021/acs.inorgchem.9b01931	journal	September 2019
Structural criteria for the mode of bonding of organoactinides and -lanthanides and related compounds Raymond, Kenneth N.; Eigenbrot, Charles W. Accounts of Chemical Research, Vol. 13, Issue 8 https://doi.org/10.1021/ar50152a005	journal	August 1980
Complexation and Separation of Lanthanides(III) and Actinides(III) by Heterocyclic N-Donors in Solutions Kolarik, Zdenek Chemical Reviews, Vol. 108, Issue 10 https://doi.org/10.1021/cr078003i	journal	October 2008
Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products Knope, Karah E.; Soderholm, L. Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300212f	journal	October 2012
Recent Advances in Aqueous Actinide Chemistry and Thermodynamics Altmaier, Marcus; Gaona, Xavier; Fanghänel, Thomas Chemical Reviews, Vol. 113, Issue 2 https://doi.org/10.1021/cr300379w	journal	October 2012
Thermodynamic Study of the Complexation of Trivalent Actinide and Lanthanide Cations by ADPTZ, a Tridentate N-Donor Ligand Miguirditchian, Manuel; Guillaneux, Denis; Guillaumont, Dominique Inorganic Chemistry, Vol. 44, Issue 5 https://doi.org/10.1021/ic0488785	journal	March 2005
Characterization and Comparison of Cm(III) and Eu(III) Complexed with 2,6-Di(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine Using EXAFS, TRFLS, and Quantum-Chemical Methods Denecke, Melissa A.; Rossberg, André; Panak, Petra J. Inorganic Chemistry, Vol. 44, Issue 23 https://doi.org/10.1021/ic0511726	journal	November 2005
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
Lanthanide N , N -Dimethylaminodiboranates as a New Class of Highly Volatile Chemical Vapor Deposition Precursors Daly, Scott R.; Kim, Do Young; Girolami, Gregory S. Inorganic Chemistry, Vol. 51, Issue 13 https://doi.org/10.1021/ic201852j	journal	June 2012
Does Covalency Increase or Decrease across the Actinide Series? Implications for Minor Actinide Partitioning Kaltsoyannis, Nikolas Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3006025	journal	June 2012
Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides Hudson, Michael J.; Harwood, Laurence M.; Laventine, Dominic M. Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic3008848	journal	June 2012
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
Comparison of Two Tetrapodal N,O Ligands: Impact of the Softness of the Heterocyclic N-Donors Pyridine and Pyrazine on the Selectivity for Am(III) over Eu(III) Heitzmann, Marie; Bravard, Florence; Gateau, Christelle Inorganic Chemistry, Vol. 48, Issue 1 https://doi.org/10.1021/ic8017024	journal	January 2009
An Ion-exchange Study of Possible Hybridized 5f Bonding in the Actinides ¹ Diamond, R. M.; Street, K.; Seaborg, G. T. Journal of the American Chemical Society, Vol. 76, Issue 6 https://doi.org/10.1021/ja01635a001	journal	March 1954
Comparison of Covalency in the Complexes of Trivalent Actinide and Lanthanide Cations Jensen, Mark P.; Bond, Andrew H. Journal of the American Chemical Society, Vol. 124, Issue 33 https://doi.org/10.1021/ja0178620	journal	August 2002
Covalency in Lanthanides. An X-ray Absorption Spectroscopy and Density Functional Theory Study of LnCl ₆ ^{x –} ( x = 3, 2) Löble, Matthias W.; Keith, Jason M.; Altman, Alison B. Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja510067v	journal	February 2015
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
On the Origin of Covalent Bonding in Heavy Actinides Kelley, Morgan P.; Su, Jing; Urban, Matthew Journal of the American Chemical Society, Vol. 139, Issue 29 https://doi.org/10.1021/jacs.7b03251	journal	July 2017
Covalency in Americium(III) Hexachloride Cross, Justin N.; Su, Jing; Batista, Enrique R. Journal of the American Chemical Society, Vol. 139, Issue 25 https://doi.org/10.1021/jacs.7b03755	journal	June 2017
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
Crystal structures of (MeC5H4)3ML [M = uranium or cerium; L = quinuclidine or P(OCH2)3CEt]. Evidence for uranium to phosphorus .pi.-back-bonding Brennan, John G.; Stults, Stephen D.; Andersen, Richard A. Organometallics, Vol. 7, Issue 6 https://doi.org/10.1021/om00096a016	journal	June 1988
The Bond between CO and Cp′ ₃ U in Cp′ ₃ U(CO) Involves Back-bonding from the Cp′ ₃ U Ligand-Based Orbitals of π-Symmetry, where Cp′ Represents a Substituted Cyclopentadienyl Ligand Maron, Laurent; Eisenstein, Odile; Andersen, Richard A. Organometallics, Vol. 28, Issue 13 https://doi.org/10.1021/om801098b	journal	July 2009
Actinide covalency measured by pulsed electron paramagnetic resonance spectroscopy Formanuik, Alasdair; Ariciu, Ana-Maria; Ortu, Fabrizio Nature Chemistry, Vol. 9, Issue 6 https://doi.org/10.1038/nchem.2692	journal	December 2016
Lanthanide( iii )/actinide( iii ) differentiation in coordination of azine molecules to tris(cyclopentadienyl) complexes of cerium and uranium Mehdoui, Thouraya; Berthet, Jean-Claude; Thuéry, Pierre Dalton Trans., Issue 4 https://doi.org/10.1039/B313992A	journal	January 2004
Probing the difference in covalence by enthalpy measurements: a new heterocyclic N-donor ligand for actinide/lanthanide separation Yang, Yanqiu; Liu, Jun; Yang, Liang Dalton Transactions, Vol. 44, Issue 19 https://doi.org/10.1039/C5DT00679A	journal	January 2015
The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study Lukens, W. W.; Speldrich, M.; Yang, P. Dalton Transactions, Vol. 45, Issue 28 https://doi.org/10.1039/C6DT00634E	journal	January 2016
Quantification of f-element covalency through analysis of the electron density: insights from simulation Kerridge, A. Chemical Communications, Vol. 53, Issue 50 https://doi.org/10.1039/C7CC00962C	journal	January 2017
Ligands for f-element extraction used in the nuclear fuel cycle Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem Chemical Society Reviews, Vol. 46, Issue 23 https://doi.org/10.1039/C7CS00574A	journal	January 2017
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
Chemical structure and bonding in a thorium( iii )–aluminum heterobimetallic complex Altman, Alison B.; Brown, Alexandra C.; Rao, Guodong Chemical Science, Vol. 9, Issue 18 https://doi.org/10.1039/C8SC01260A	journal	January 2018
Automated exploration of the low-energy chemical space with fast quantum chemical methods Pracht, Philipp; Bohle, Fabian; Grimme, Stefan Physical Chemistry Chemical Physics, Vol. 22, Issue 14 https://doi.org/10.1039/C9CP06869D	journal	January 2020
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient Klamt, A.; Schüürmann, G. J. Chem. Soc., Perkin Trans. 2, Issue 5 https://doi.org/10.1039/P29930000799	journal	January 1993
The remarkable efficiency of N-heterocyclic carbenes in lanthanide(iii)/actinide(iii) differentiation Mehdoui, Thouraya; Berthet, Jean-Claude; Thuéry, Pierre Chemical Communications, Issue 22 https://doi.org/10.1039/b503526k	journal	January 2005
The vitality of uranium molecular chemistry at the dawn of the XXIst century Ephritikhine, Michel Dalton Transactions, Issue 21 https://doi.org/10.1039/b603463b	journal	January 2006
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
Evidence for covalence in a N-donor complex of americium(iii) Adam, Christian; Kaden, Peter; Beele, Björn B. Dalton Transactions, Vol. 42, Issue 39 https://doi.org/10.1039/c3dt50953b	journal	January 2013
The chemistry of the trivalent actinides. Part II. Uranium(III) double chlorides and some complexes with oxygen-donor ligands Barnard, R.; Bullock, J. I.; Gellatly, B. J. Journal of the Chemical Society, Dalton Transactions, Issue 18 https://doi.org/10.1039/dt9720001932	journal	January 1972
Accurate and simple analytic representation of the electron-gas correlation energy Perdew, John P.; Wang, Yue Physical Review B, Vol. 45, Issue 23, p. 13244-13249 https://doi.org/10.1103/PhysRevB.45.13244	journal	June 1992
Climbing the Density Functional Ladder: Nonempirical Meta–Generalized Gradient Approximation Designed for Molecules and Solids Tao, Jianmin; Perdew, John P.; Staroverov, Viktor N. Physical Review Letters, Vol. 91, Issue 14 https://doi.org/10.1103/PhysRevLett.91.146401	journal	September 2003
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
Competing Metal–Ligand Interactions in Tris(cyclopentadienyl)-cyclohexylisonitrile Complexes of Trivalent Actinides and Lanthanides Kovács, Attila; Apostolidis, Christos; Walter, Olaf Molecules, Vol. 27, Issue 12 https://doi.org/10.3390/molecules27123811	journal	June 2022