A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents

Stein, Benjamin W.; Cary, Samantha K.; Berg, John M.; Birnbaum, Eva R.; Kozimor, Stosh Anthony; Mocko, Veronika; Scott, Brian Lindley

doi:10.1016/j.jorganchem.2017.11.026

A Series of F-Element Chelators; Diaza Crown Ethers Functionalized with Catecholate Binding Substituents

Journal Article · Wed Dec 06 00:00:00 EST 2017 · Journal of Organometallic Chemistry

DOI:https://doi.org/10.1016/j.jorganchem.2017.11.026· OSTI ID:1412875

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Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Here, we report on the preparation of azacrown ethers functionalized with catechol groups. The synthetic approach was (1st) novel in that it made use of the Mannich reaction and (2nd) valuable in that it provided an improved synthesis (in terms of practical deployment) of the known N,N'-bis(2,3-dihydroxybenzyl)-4,13-diaza-18-crown-6, H₄ChaCha. Moreover, it demonstrated potential application of the synthetic method for accommodating a wide range of catecholate functionalities by using the synthetic strategy to prepare N,N'-bis(2,3-dihydroxy-5-tert-butylbenzyl)-4,13-diaza-18-crown-6 (H₄^tBu₂ChaCha) for the first time. These H₄ChaCha and H₄^tBu2ChaCha macrocycles offer exciting opportunity to expand redox chemistry for the f-elements. As “proof-of-principle,” we isolated the unusual tetrameric cluster [La₂(^tBuChaCha)₂]₂ from reactions between H₄^tBu₂ChaCha and La[N(SiMe₃)₂]₃. Characterization of [La₂(^tBuChaCha)₂]₂ by elemental analysis, single crystal X-ray diffraction, IR, and UV–vis–NIR spectroscopy suggested that the complex represented a rare example of an f-element semiquinone. It further demonstrated that the combination of La³⁺ and H₄^tBu₂ChaCha provided access to one-electron oxidation chemistry within redox potential windows that were amenable to mild reaction conditions.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL)

Sponsoring Organization:: USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC52-06NA25396

OSTI ID:: 1412875

Alternate ID(s):: OSTI ID: 1548919

Report Number(s):: LA-UR-17-28162

Journal Information:: Journal of Organometallic Chemistry, Journal Name: Journal of Organometallic Chemistry Vol. 857; ISSN 0022-328X

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (53)

Antiferromagnetic Coupling in a Gadolinium(III) Semiquinonato Complex Caneschi, Andrea; Dei, Andrea; Gatteschi, Dante Angewandte Chemie International Edition, Vol. 39, Issue 1 https://doi.org/10.1002/(SICI)1521-3773(20000103)39:1<246::AID-ANIE246>3.0.CO;2-B	journal	January 2000
Spontaneous Symmetry Breaking in the Formation of a Dinuclear Gadolinium Semiquinonato Complex: Synthesis, High-Field EPR Studies, and Magnetic Properties Dei, Andrea; Gatteschi, Dante; Massa, Carlo A. Chemistry, Vol. 6, Issue 24 https://doi.org/10.1002/1521-3765(20001215)6:24<4580::AID-CHEM4580>3.0.CO;2-B	journal	December 2000
Neodymium(III) Complexes Capable of Multi-Electron Redox Chemistry Coughlin, Ezra J.; Zeller, Matthias; Bart, Suzanne C. Angewandte Chemie International Edition, Vol. 56, Issue 40 https://doi.org/10.1002/anie.201705423	journal	August 2017
Electro-kinetic Separation of Rare Earth Elements Using a Redox-Active Ligand Fang, Huayi; Cole, Bren E.; Qiao, Yusen Angewandte Chemie International Edition, Vol. 56, Issue 43 https://doi.org/10.1002/anie.201706894	journal	September 2017
The First Lanthanide Complexes with a Redox-Active Sulfur Diimide Ligand: Synthesis and Characterization of [LnCp* ₂ (RN=) ₂ S], Ln=Sm, Eu, Yb; R=SiMe ₃ Klementyeva, Svetlana V.; Gritsan, Nina P.; Khusniyarov, Marat M. Chemistry - A European Journal, Vol. 23, Issue 6 https://doi.org/10.1002/chem.201604340	journal	December 2016
Synthesis of N ‐pivot lariat ethers Elwahy, Ahmed H. M.; Abbas, Ashraf A. Journal of Heterocyclic Chemistry, Vol. 45, Issue 1 https://doi.org/10.1002/jhet.5570450101	journal	January 2008
Achieving new lanthanide chemistry within the tetracyclopentadienyl cavity formed by two (C5Me5)2Ln moieties Evans, William J. Journal of Alloys and Compounds, Vol. 192, Issue 1-2 https://doi.org/10.1016/0925-8388(93)90231-B	journal	February 1993
Synthesis of chromogenic crown ethers and liquid-liquid extraction of alkali metal ions Katayama, Yoshiki; Nita, Kazuhide; Ueda, Masahide Analytica Chimica Acta, Vol. 173 https://doi.org/10.1016/S0003-2670(00)84957-0	journal	January 1985
Synthesis of chromogenic crown ethers and liquid—liquid extraction of alkaline earth metal ions Katayama, Yoshiki; Fukuda, Ryuji; Iwasaki, Toshiharu Analytica Chimica Acta, Vol. 204 https://doi.org/10.1016/S0003-2670(00)86350-3	journal	January 1988
Transition metal complexes of o-benzoquinone, o-semiquinone, and catecholate ligands Pierpont, Cortlandt G.; Buchanan, Robert M. Coordination Chemistry Reviews, Vol. 38, Issue 1 https://doi.org/10.1016/S0010-8545(00)80499-3	journal	August 1981
Studies on charge distribution and valence tautomerism in transition metal complexes of catecholate and semiquinonate ligands Pierpont, Cortlandt G. Coordination Chemistry Reviews, Vol. 216-217 https://doi.org/10.1016/S0010-8545(01)00309-5	journal	June 2001
Coordination chemistry of lanthanide catecholates Zhu, Dao-Hong; Kappel, Mary J.; Raymond, Kenneth N. Inorganica Chimica Acta, Vol. 147, Issue 1 https://doi.org/10.1016/S0020-1693(00)80639-8	journal	July 1988
Synthesis, structure and reactivity of organometallic complexes of Sm(II) Evans, William J. Inorganica Chimica Acta, Vol. 139, Issue 1-2 https://doi.org/10.1016/S0020-1693(00)84070-0	journal	December 1987
Actinide-specific complexing agents: Their structural and solution chemistry Raymond, Kenneth N.; Freeman, Gwen E.; Kappel, Mary J. Inorganica Chimica Acta, Vol. 94, Issue 4 https://doi.org/10.1016/S0020-1693(00)88005-6	journal	April 1984
Complexation of thorium(IV) by tris((2,3-dihydroxybenzylamino)ethyl)amine—a new strong chelating agent Bismondo, Arturo; Comuzzi, Clara; Di Bernardo, Plinio Inorganica Chimica Acta, Vol. 286, Issue 1 https://doi.org/10.1016/S0020-1693(98)00376-4	journal	March 1999
The expansion of divalent organolanthanide reduction chemistry via new molecular divalent complexes and sterically induced reduction reactivity of trivalent complexes Evans, William J. Journal of Organometallic Chemistry, Vol. 647, Issue 1-2 https://doi.org/10.1016/S0022-328X(01)01462-0	journal	March 2002
Recent advances in f element reduction chemistry Evans, William J. Journal of Organometallic Chemistry, Vol. 652, Issue 1-2 https://doi.org/10.1016/S0022-328X(02)01308-6	journal	June 2002
Borocryptands : Synthesis and Structural Analysis of a Lithium Borocryptate Bockstahl, Frédéric; Graf, Ernest; Hosseini, Mir Wais Tetrahedron Letters, Vol. 38, Issue 43 https://doi.org/10.1016/S0040-4039(97)10026-0	journal	October 1997
The organometallic Chemistry of the lanthanide elements in low oxidation states Evans, William J. Polyhedron, Vol. 6, Issue 5 https://doi.org/10.1016/S0277-5387(00)80921-3	journal	January 1987
Complexation of lanthanide(III) with a tripodal polyaza polycatecholate ligand Bismondo, Arturo; Di Bernardo, Plinio; Portanova, Roberto Polyhedron, Vol. 21, Issue 14-15 https://doi.org/10.1016/S0277-5387(02)00962-2	journal	June 2002
Expanding the chemistry of U3+ reducing agents Evans, W.; Kozimor, S. Coordination Chemistry Reviews, Vol. 250, Issue 7-8 https://doi.org/10.1016/j.ccr.2006.01.017	journal	April 2006
Advances in f element reductive reactivity as a paradigm for expanding lanthanide and actinide science and technology Evans, William J. Journal of Alloys and Compounds, Vol. 488, Issue 2 https://doi.org/10.1016/j.jallcom.2009.02.018	journal	December 2009
3,5-Di-tert-butyl-o-benzoquinone complexes of lanthanides Kuzyaev, D. M.; Vorozhtsov, D. L.; Druzhkov, N. O. Journal of Organometallic Chemistry, Vol. 698 https://doi.org/10.1016/j.jorganchem.2011.10.015	journal	February 2012
Potentiometric, spectrophotometric, theoretical studies and binding properties of a novel tripodal polycatechol-amine ligand with lanthanide(III) ions Sahoo, Suban K.; Baral, Minati; Kanungo, B. K. Polyhedron, Vol. 25, Issue 3 https://doi.org/10.1016/j.poly.2005.07.039	journal	February 2006
Electrochemistry of Corroles in Nonaqueous Media Fang, Yuanyuan; Ou, Zhongping; Kadish, Karl M. Chemical Reviews, Vol. 117, Issue 4 https://doi.org/10.1021/acs.chemrev.6b00546	journal	November 2016
Tutorial on the Role of Cyclopentadienyl Ligands in the Discovery of Molecular Complexes of the Rare-Earth and Actinide Metals in New Oxidation States Evans, William J. Organometallics, Vol. 35, Issue 18 https://doi.org/10.1021/acs.organomet.6b00466	journal	September 2016
Thermodynamic and Kinetic Data for Macrocycle Interaction with Cations, Anions, and Neutral Molecules Izatt, Reed M.; Pawlak, Krystyna.; Bradshaw, Jerald S. Chemical Reviews, Vol. 95, Issue 7 https://doi.org/10.1021/cr00039a010	journal	November 1995
Synthesis of aza-crown ethers Krakowiak, Krzysztof E.; Bradshaw, Jerald S.; Zamecka-Krakowiak, Daria J. Chemical Reviews, Vol. 89, Issue 4 https://doi.org/10.1021/cr00094a008	journal	June 1989
Chemistry of Tris(pentamethylcyclopentadienyl) f-Element Complexes, (C ₅ Me ₅ ) ₃ M Evans, William J.; Davis, Benjamin L. Chemical Reviews, Vol. 102, Issue 6 https://doi.org/10.1021/cr010298r	journal	June 2002
Therapeutic Radiopharmaceuticals Volkert, Wynn A.; Hoffman, Timothy J. Chemical Reviews, Vol. 99, Issue 9 https://doi.org/10.1021/cr9804386	journal	September 1999
Rational Design of Sequestering Agents for Plutonium and Other Actinides Gorden, Anne E. V.; Xu, Jide; Raymond, Kenneth N. Chemical Reviews, Vol. 103, Issue 11 https://doi.org/10.1021/cr990114x	journal	November 2003
Equilibrium and kinetic studies of lanthanide complexes of macrocyclic polyamino carboxylates Kumar, Krishan; Chang, C. Allen; Tweedle, M. F. Inorganic Chemistry, Vol. 32, Issue 5 https://doi.org/10.1021/ic00057a017	journal	March 1993
Specific sequestering agents for the actinides. 12. Synthetic and structural chemistry of gadolinium and holmium catecholates Freeman, Gwen E.; Raymond, Kenneth N. Inorganic Chemistry, Vol. 24, Issue 9 https://doi.org/10.1021/ic00203a029	journal	April 1985
Lanthanide Dinuclear Complexes Involving Tetrathiafulvalene-3-pyridine-N-oxide Ligand: Semiconductor Radical Salt, Magnetic, and Photophysical Studies Pointillart, Fabrice; Guennic, Boris Le; Maury, Olivier Inorganic Chemistry, Vol. 52, Issue 3 https://doi.org/10.1021/ic302095h	journal	January 2013
Nuclear magnetic resonance spectroscopy of lanthanide complexes with a tetraacetic tetraaza macrocycle. Unusual conformation properties Desreux, J. F. Inorganic Chemistry, Vol. 19, Issue 5 https://doi.org/10.1021/ic50207a042	journal	May 1980
Redox chemistry of metal-catechol complexes in aprotic media. 1. Electrochemistry of substituted catechols and their oxidation products Stallings, Martin D.; Morrison, Mark M.; Sawyer, Donald T. Inorganic Chemistry, Vol. 20, Issue 8 https://doi.org/10.1021/ic50222a053	journal	August 1981
Trapping of Anionic Organic Radicals by (Tp ^Me2 ) ₂ Ln (Ln = Sm, Eu) Domingos, Ângela; Lopes, Irene; Waerenborgh, João C. Inorganic Chemistry, Vol. 46, Issue 22 https://doi.org/10.1021/ic701364k	journal	October 2007
Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide and Lanthanoid-Actinide Complexes Possessing Redox-Active Bridging Ligands Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M. Inorganic Chemistry, Vol. 49, Issue 4 https://doi.org/10.1021/ic9024475	journal	February 2010
Potentiometric, Calorimetric, and Solution NMR Studies of a Tridentate Ligand Which has a Marked Preference for Formation of Bis(ligand) versus Mono(ligand) Lanthanide Complexes and Which Exhibits High Selectivity for Heavier Lanthanides Caravan, P.; Hedlund, Tomas; Liu, Shuang Journal of the American Chemical Society, Vol. 117, Issue 45 https://doi.org/10.1021/ja00150a021	journal	November 1995
Bis(dioxolene)(bipyridine)ruthenium redox series Lever, A. B. P.; Auburn, Pamela R.; Dodsworth, Elaine S. Journal of the American Chemical Society, Vol. 110, Issue 24 https://doi.org/10.1021/ja00232a020	journal	November 1988
Electrochemically switched cation binding in nitrobenzene-substituted, nitrogen-pivot lariat ethers Gustowski, Deborah A.; Echegoyen, Luis; Goli, Deepa M. Journal of the American Chemical Society, Vol. 106, Issue 6 https://doi.org/10.1021/ja00318a014	journal	March 1984
Protection of hydroxyl groups as tert-butyldimethylsilyl derivatives Corey, E. J.; Venkateswarlu, A. Journal of the American Chemical Society, Vol. 94, Issue 17 https://doi.org/10.1021/ja00772a043	journal	August 1972
Cyclic polyethers and their complexes with metal salts Pedersen, Charles J. Journal of the American Chemical Society, Vol. 89, Issue 26 https://doi.org/10.1021/ja01002a035	journal	December 1967
A Macrocyclic Chelator with Unprecedented Th ⁴⁺ Affinity Pham, Tiffany A.; Xu, Jide; Raymond, Kenneth N. Journal of the American Chemical Society, Vol. 136, Issue 25 https://doi.org/10.1021/ja503456r	journal	June 2014
Arene-Bridged Diuranium Complexes: Inverted Sandwiches Supported by δ Backbonding Diaconescu, Paula L.; Arnold, Polly L.; Baker, Thomas A. Journal of the American Chemical Society, Vol. 122, Issue 25 https://doi.org/10.1021/ja994484e	journal	June 2000
A New One-Pot Synthesis of Double-Armed Ionizable Crown Ethers Using the Mannich Reaction Chi, Ki-Whan; Wei, Han-Chao; Kottke, Thomas The Journal of Organic Chemistry, Vol. 61, Issue 16 https://doi.org/10.1021/jo960332f	journal	January 1996
An Efficient Route to Alkyl Chlorides from Alcohols Using the Complex TCT/DMF De Luca, Lidia; Giacomelli, Giampaolo; Porcheddu, Andrea Organic Letters, Vol. 4, Issue 4 https://doi.org/10.1021/ol017168p	journal	February 2002
Multielectron redox chemistry of lanthanide Schiff-base complexes Camp, Clément; Guidal, Valentin; Biswas, Biplab Chemical Science, Vol. 3, Issue 8 https://doi.org/10.1039/C2SC20476B	journal	January 2012
Exchange coupling and magnetic blocking in dilanthanide complexes bridged by the multi-electron redox-active ligand 2,3,5,6-tetra(2-pyridyl)pyrazine Demir, Selvan; Nippe, Michael; Gonzalez, Miguel I. Chem. Sci., Vol. 5, Issue 12 https://doi.org/10.1039/C4SC02154A	journal	January 2014
Cooperative reduction by Ln ²⁺ and Cp* ⁻ ions: synthesis and properties of Sm, Eu, and Yb complexes with 3,6-di-tert-butyl-o-benzoquinone Pushkarevsky, Nikolay A.; Ogienko, Mikhail A.; Smolentsev, Anton I. Dalton Transactions, Vol. 45, Issue 3 https://doi.org/10.1039/C5DT03573B	journal	January 2016
Protonation and lanthanide(iii) complexation equilibria of a new tripodal polyaza-polycatechol-amine Di Bernardo, P.; Zanonato, P. L.; Bismondo, A. Dalton Transactions, Issue 21 https://doi.org/10.1039/b822945g	journal	January 2009
Lariat ethers. Synthesis and cation binding of macrocyclic polyethers possessing axially disposed secondary donor groups Gokel, George W.; Dishong, Dennis M.; Diamond, Craig J. Journal of the Chemical Society, Chemical Communications, Issue 22 https://doi.org/10.1039/c39800001053	journal	January 1980
Lariat ethers: from simple sidearms to supramolecular systems Gokel, George W. Chemical Society Reviews, Vol. 21, Issue 1 https://doi.org/10.1039/cs9922100039	journal	January 1992

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