Unsaturated Sulfur Crown Ethers Can Extract Mercury(II) and Show Promise for Future Copernicium(II) Studies: A Combined Experimental and Computational Study

Ferrier, Maryline G.; Valdez, Carlos A.; Singh, Saurabh Kumar; Hok, Saphon; Ray, Debmalya; Gagliardi, Laura; Despotopulos, John D.

doi:10.1021/acs.inorgchem.1c01869

Title: Unsaturated Sulfur Crown Ethers Can Extract Mercury(II) and Show Promise for Future Copernicium(II) Studies: A Combined Experimental and Computational Study

Journal Article · 28 December 2021 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.1c01869 · OSTI ID:1864681

^[1]; Valdez, Carlos A. ^[2];

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Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory (LLNL), 7000 East Avenue, Livermore, California 94550, United States
Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory (LLNL), 7000 East Avenue, Livermore, California 94550, United States; Forensic Science Center, Lawrence Livermore National Laboratory (LLNL), 7000 East Avenue, Livermore, California 94550, United States
Department of Chemistry, Indian Institute of Technology (IIT) Hyderabad, Kandi, Sangareddy 502285, Telangana, India
Department of Chemistry, Chemical Theory Center and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455, United States
Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute, Chicago Center for Theoretical Chemistry, The University of Chicago, 5735 S Ellis Avenue, Chicago, Illinois 60637, United States; Argonne National Laboratory, 97000 South Cass Avenue, Lemont, Illinois 60439, United States

The unsaturated hexathia-18-crown-6 (UHT18C6) molecule was investigated for the extraction of Hg(II) in HCl and HNO3 media. This extractant can be directly compared to the recently studied saturated hexathia-18-crown-6 (HT18C6). The default conformation of the S lone pairs in UHT18C6 is endodentate, where the pocket of the charge density, according to the crystal structures, is oriented toward the center of the ring, which should allow better extraction for Hg(II) compared to the exodentate HT18C6. Batch study experiments showed that Hg(II) had better extraction at low acid molarity (ca. 99% in HCl and ca. 95% in HNO₃), while almost no extraction was observed above 0.4 M HCl and 4 M HNO₃ (<5%). Speciation studies were conducted with the goal of delineating a plausible extraction mechanism. Density functional theory calculations including relativistic effects were carried out on both Hg(II)-encapsulated HT18C6 and UHT18C6 complexes to shed light on the binding strength and the nature of bonding. Our calculations offer insights into the extraction mechanism. In addition to Hg(II), calculations were performed on the hypothetical divalent Cn(II) ion, and showed that HT18C6 and UHT18C6 could extract Cn(II). Finally, the extraction kinetics were explored to assess whether this crown can extract the short-lived Cn(II) species in a future online experiment.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-06CH11357; AC52-07NA27344; NA0003180

OSTI ID:: 1864681

Report Number(s):: LLNL-JRNL-823071; 173739

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 2 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (38)

Is Eka-Mercury (Element 112) a Group 12 Metal? Gaston, Nicola; Opahle, Ingo; Gäggeler, Heinz W. Angewandte Chemie International Edition, Vol. 46, Issue 10 https://doi.org/10.1002/anie.200604262	journal	February 2007
Copernicium: A Relativistic Noble Liquid Mewes, Jan‐Michael; Smits, Odile R.; Kresse, Georg Angewandte Chemie International Edition, Vol. 58, Issue 50 https://doi.org/10.1002/anie.201906966	journal	December 2019
The Valence States of Copernicium and Flerovium: The Valence States of Copernicium and Flerovium Ghosh, Abhik; Conradie, Jeanet European Journal of Inorganic Chemistry, Vol. 2016, Issue 18 https://doi.org/10.1002/ejic.201600146	journal	May 2016
Optimized Slater-type basis sets for the elements 1-118 Van Lenthe, E.; Baerends, E. J. Journal of Computational Chemistry, Vol. 24, Issue 9 https://doi.org/10.1002/jcc.10255	journal	May 2003
Chemistry with ADF te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J. Journal of Computational Chemistry, Vol. 22, Issue 9, p. 931-967 https://doi.org/10.1002/jcc.1056	journal	January 2001
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
An implementation of the conductor-like screening model of solvation within the Amsterdam density functional package Pye, Cory C.; Ziegler, Tom Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 101, Issue 6 https://doi.org/10.1007/s002140050457	journal	May 1999
Production and isolation of 197m,gHg Despotopulos, John D.; Kmak, Kelly N.; Shaughnessy, Dawn A. Journal of Radioanalytical and Nuclear Chemistry, Vol. 317, Issue 2 https://doi.org/10.1007/s10967-018-5927-9	journal	June 2018
Transactinide studies with sulfur macrocyclic extractant using mercury Ferrier, Maryline G.; Kmak, Kelly N.; Kerlin, William M. Journal of Radioanalytical and Nuclear Chemistry, Vol. 326, Issue 1 https://doi.org/10.1007/s10967-020-07320-4	journal	August 2020
Macrocyclic polythiaethers as solvent extraction reagents—III Sevdić, D.; Fekete, L.; Meider, H. Journal of Inorganic and Nuclear Chemistry, Vol. 42, Issue 6 https://doi.org/10.1016/0022-1902(80)80462-3	journal	January 1980
Macrocyclic polythiaethers as solvent extraction reagents—IV Ag(I) and Hg(II) complexes with 1,4,7,10,13,16-hexathiacyclooctadecane Sevdić, D.; Meider, H. Journal of Inorganic and Nuclear Chemistry, Vol. 43, Issue 1 https://doi.org/10.1016/0022-1902(81)80452-6	journal	January 1981
The stability constants of the aqueous chloro complexes of divalent zinc, cadmium and mercury determined by solvent extraction with tri-n-octylphosphine oxide Sato, Taichi; Nakamura, Takato Hydrometallurgy, Vol. 6, Issue 1-2 https://doi.org/10.1016/0304-386X(80)90003-1	journal	September 1980
Intermetallic compounds of the heaviest elements: the electronic structure and bonding of dimers of element 112 and its homolog Hg Pershina, V.; Bastug, T.; Jacob, T. Chemical Physics Letters, Vol. 365, Issue 1-2 https://doi.org/10.1016/S0009-2614(02)01428-8	journal	October 2002
Relativistic effects on experimentally studied gas-phase properties of the heaviest elements Pershina, V.; Bastug, T. Chemical Physics, Vol. 311, Issue 1-2 https://doi.org/10.1016/j.chemphys.2004.09.030	journal	April 2005
Chemical and nuclear studies of hassium and element 112 Ga¨ggeler, H. W.; Bru¨chle, W.; Du¨llmann, Ch. E. Nuclear Physics A, Vol. 734 https://doi.org/10.1016/j.nuclphysa.2004.01.036	journal	April 2004
OPLS3: A Force Field Providing Broad Coverage of Drug-like Small Molecules and Proteins Harder, Edward; Damm, Wolfgang; Maple, Jon Journal of Chemical Theory and Computation, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jctc.5b00864	journal	December 2015
Unsaturated Thiacrown Ethers: Synthesis, Physical Properties, and Formation of a Silver Complex Tsuchiya, Takahiro; Shimizu, Toshio; Kamigata, Nobumasa Journal of the American Chemical Society, Vol. 123, Issue 47 https://doi.org/10.1021/ja0102742	journal	October 2001
Formation and Structures of Mercury Complexes of 18-Membered Unsaturated and Saturated Thiacrown Ethers Tsuchiya, Takahiro; Shimizu, Toshio; Hirabayashi, Kazunori The Journal of Organic Chemistry, Vol. 68, Issue 9 https://doi.org/10.1021/jo020668r	journal	May 2003
Chemical characterization of element 112 Eichler, R.; Aksenov, N. V.; Belozerov, A. V. Nature, Vol. 447, Issue 7140 https://doi.org/10.1038/nature05761	journal	May 2007
Exploring the chemical nature of super-heavy main-group elements by means of efficient plane-wave density-functional theory Trombach, Lukas; Ehlert, Sebastian; Grimme, Stefan Physical Chemistry Chemical Physics, Vol. 21, Issue 33 https://doi.org/10.1039/C9CP02455G	journal	January 2019
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
Polymer pendant crown thioethers: synthesis and HgII extraction studies of a novel thiacrown polymer Baumann, Theodore F.; Reynolds, John G. Chemical Communications, Issue 16 https://doi.org/10.1039/a803383h	journal	January 1998
An Economical Approach to the Synthesis of Unsaturated Thiacrown Ethers Sun, Dong-Qing; Yang, Jing-Kui Synthesis, Vol. 2011, Issue 15 https://doi.org/10.1055/s-0030-1260066	journal	June 2011
Adsorption of superheavy elements on metal surfaces Sarpe-Tudoran, C.; Fricke, B.; Anton, J. The Journal of Chemical Physics, Vol. 126, Issue 17 https://doi.org/10.1063/1.2727447	journal	May 2007
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Are elements 112, 114, and 118 relatively inert gases? Pitzer, Kenneth S. The Journal of Chemical Physics, Vol. 63, Issue 2 https://doi.org/10.1063/1.431398	journal	July 1975
Relativistic regular two‐component Hamiltonians Lenthe, E. van; Baerends, E. J.; Snijders, J. G. The Journal of Chemical Physics, Vol. 99, Issue 6 https://doi.org/10.1063/1.466059	journal	September 1993
The chemistry of the superheavy elements. I. Pseudopotentials for 111 and 112 and relativistic coupled cluster calculations for (112)H ⁺ , (112)F ₂ , and (112)F ₄ Seth, Michael; Schwerdtfeger, Peter; Dolg, Michael The Journal of Chemical Physics, Vol. 106, Issue 9 https://doi.org/10.1063/1.473437	journal	March 1997
Mercury Extraction by the Truex Process Solvent. i. Kinetics, Extractable Species, & Dependence on Nitric acid Concentration1 Herbst, R. S.; Brewer, K. N.; Tranter, T. J. Solvent Extraction and Ion Exchange, Vol. 13, Issue 3 https://doi.org/10.1080/07366299508918284	journal	May 1995
Chemistry of the superheavy elements Schädel, Matthias Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 373, Issue 2037 https://doi.org/10.1098/rsta.2014.0191	journal	March 2015
Transition energies of mercury and ekamercury (element 112) by the relativistic coupled-cluster method Eliav, Ephraim; Kaldor, Uzi; Ishikawa, Yasuyuki Physical Review A, Vol. 52, Issue 4 https://doi.org/10.1103/PhysRevA.52.2765	journal	October 1995
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals Hammer, B.; Hansen, L. B.; Nørskov, J. K. Physical Review B, Vol. 59, Issue 11 https://doi.org/10.1103/PhysRevB.59.7413	journal	March 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Comment on “Generalized Gradient Approximation Made Simple” Zhang, Yingkai; Yang, Weitao Physical Review Letters, Vol. 80, Issue 4 https://doi.org/10.1103/PhysRevLett.80.890	journal	January 1998
Tetrabromo(1,4,7,10,13,16-hexathiacyclooctadecane)dimercury(II) Herceg, M.; Matković-Čalogović, D. Acta Crystallographica Section C Crystal Structure Communications, Vol. 48, Issue 10 https://doi.org/10.1107/S0108270192002671	journal	October 1992
Chemical speciation of environmentally significant heavy metals with inorganic ligands. Part 1: The Hg2+– Cl–, OH–, CO32–, SO42–, and PO43– aqueous systems (IUPAC Technical Report) Powell, Kipton J.; Brown, Paul L.; Byrne, Robert H. Pure and Applied Chemistry, Vol. 77, Issue 4 https://doi.org/10.1351/pac200577040739	journal	January 2005
First attempt to chemically identify element 112 Yakushev, Alexander B.; Buklanov, G. V.; Chelnokov, M. L. Radiochimica Acta, Vol. 89, Issue 11-12 https://doi.org/10.1524/ract.2001.89.11-12.743	journal	November 2001
Chemical identification and properties of element 112 Yakushev, Alexander B.; Zvara, I.; Oganessian, Yu. Ts. Radiochimica Acta, Vol. 91, Issue 8 https://doi.org/10.1524/ract.91.8.433.20010	journal	August 2003

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Title: Unsaturated Sulfur Crown Ethers Can Extract Mercury(II) and Show Promise for Future Copernicium(II) Studies: A Combined Experimental and Computational Study

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