Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

Kumar, Amit; Lionetti, Davide; Day, Victor W.; Blakemore, James D.

doi:10.1021/jacs.9b11903

Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

Journal Article · Mon Jan 13 04:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.9b11903· OSTI ID:1600028

Kumar, Amit ^[1]; Lionetti, Davide ^[2]; Day, Victor W. ^[2]; ^[2]

Univ. of Kansas, Lawrence, KS (United States); University of Kansas, Lawrence, KS, United States
Univ. of Kansas, Lawrence, KS (United States)

Capture and activation of the water-soluble uranyl dication (UO₂²⁺) remains a challenging problem, as few rational approaches are available for modulating the reactivity of this species. Here, we report the divergent synthesis of heterobimetallic complexes in which UO₂²⁺ is held in close proximity to a range of redox-inactive metals by a tailored macrocyclic ligand. Crystallographic and spectroscopic studies confirm assembly of homologous U^VI(μ-O_Ar)₂Mⁿ⁺ cores with a range of mono-, di-, and tri-valent Lewis acids (Mⁿ⁺). Cyclic voltammetry data demonstrate that the U^VI/U^V reduction potential in these com-plexes is modulated over a span of 600 mV, depending linearly on the Lewis acidity of the redox-inactive metal with a sensitivity of 61±9 mV/pK_a unit. These findings suggest that interactions with Lewis acids could be effectively leveraged for rational tuning of the electronic and thermochemical properties of the 5f elements, reminiscent of strategies more commonly employed with 3d transition metals.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Kansas, Lawrence, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0019169

OSTI ID:: 1600028

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 6 Vol. 142; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (42)

Elements of Molecular and Biomolecular Electrochemistry Savéant, Jean-Michel https://doi.org/10.1002/0471758078	book	January 2006
Trivalent Lewis Acidic Cations Govern the Electronic Properties and Stability of Heterobimetallic Complexes of Nickel Kumar, Amit; Lionetti, Davide; Day, Victor W. Chemistry - A European Journal, Vol. 24, Issue 1 https://doi.org/10.1002/chem.201704006	journal	November 2017
Coordination of uranyl(VI) carbonate species in aqueous solutions Meinrath, G. Journal of Radioanalytical and Nuclear Chemistry Articles, Vol. 211, Issue 2 https://doi.org/10.1007/BF02039703	journal	December 1996
Synthesis and electrochemical properties of oxo-bridged manganese dimers incorporating alkali and alkaline earth cations Horwitz, Colin P.; Ciringh, Yangzhen Inorganica Chimica Acta, Vol. 225, Issue 1-2 https://doi.org/10.1016/0020-1693(94)04047-8	journal	October 1994
Mössbauer and magnetic properties of mononuclear, homo- and hetero-dinuclear complexes Guerriero, P.; Tamburini, S.; Vigato, P. A. Inorganica Chimica Acta, Vol. 213, Issue 1-2 https://doi.org/10.1016/S0020-1693(00)83838-4	journal	November 1993
Electrochemical behaviour of acyclic and macrocyclic complexes of nickel(II), copper(II) and uranyl(VI) Zanello, P.; Cinquantini, A.; Guerriero, P. Inorganica Chimica Acta, Vol. 117, Issue 1 https://doi.org/10.1016/S0020-1693(00)88074-3	journal	July 1986
Uranyl(VI) complexes with [1+1] asymmetric compartmental ligands containing a Schiff base and a crown ether-like chamber Casellato, U.; Tamburini, S.; Tomasin, P. Inorganica Chimica Acta, Vol. 341 https://doi.org/10.1016/S0020-1693(02)01254-9	journal	December 2002
Asymmetric compartmental macrocyclic ligands and related mononuclear and hetero-dinuclear complexes with d- and/or f-metal ions Brianese, N.; Casellato, U.; Tamburini, S. Inorganica Chimica Acta, Vol. 293, Issue 2 https://doi.org/10.1016/S0020-1693(99)00235-2	journal	October 1999
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
Synthesis and study of crown ether-appended boron dipyrrin chemosensors for cation detection Blakemore, James D.; Chitta, Raghu; D’Souza, Francis Tetrahedron Letters, Vol. 48, Issue 11 https://doi.org/10.1016/j.tetlet.2007.01.067	journal	March 2007
Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. Nicholson, R. S. Analytical Chemistry, Vol. 37, Issue 11 https://doi.org/10.1021/ac60230a016	journal	October 1965
Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [U ^VI O ₂ ] ²⁺ Cowie, Bradley E.; Purkis, Jamie M.; Austin, Jonathan Chemical Reviews, Vol. 119, Issue 18 https://doi.org/10.1021/acs.chemrev.9b00048	journal	August 2019
Redox Potential and Electronic Structure Effects of Proximal Nonredox Active Cations in Cobalt Schiff Base Complexes Reath, Alexander H.; Ziller, Joseph W.; Tsay, Charlene Inorganic Chemistry, Vol. 56, Issue 6 https://doi.org/10.1021/acs.inorgchem.6b03098	journal	February 2017
Water-Splitting Chemistry of Photosystem II McEvoy, James P.; Brudvig, Gary W. Chemical Reviews, Vol. 106, Issue 11 https://doi.org/10.1021/cr0204294	journal	November 2006
Mn ₄ Ca Cluster in Photosynthesis: Where and How Water is Oxidized to Dioxygen Yano, Junko; Yachandra, Vittal Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr4004874	journal	March 2014
Electrochemical and Spectroelectrochemical Studies on UO ₂ (saloph)L (saloph = N,N ‘ -Disalicylidene- o -phenylenediaminate, L = Dimethyl Sulfoxide or N,N -Dimethylformamide) Mizuoka, Koichiro; Kim, Seong-Yun; Hasegawa, Miki Inorganic Chemistry, Vol. 42, Issue 4 https://doi.org/10.1021/ic0260926	journal	February 2003
Silylation of the Uranyl Ion Using B(C ₆ F ₅ ) ₃ -Activated Et ₃ SiH Schnaars, David D.; Wu, Guang; Hayton, Trevor W. Inorganic Chemistry, Vol. 50, Issue 19 https://doi.org/10.1021/ic201385h	journal	October 2011
Synthesis, X-ray Structure, and Solution NMR Studies of Ln(III) Complexes with a Macrocyclic Asymmetric Compartmental Schiff Base. Preference of the Ln(III) Ions for a Crown-Like Coordination Site Casellato, Umberto; Tamburini, Sergio; Tomasin, Patrizia Inorganic Chemistry, Vol. 38, Issue 12 https://doi.org/10.1021/ic980715r	journal	May 1999
Cocomplexation of neutral guests and electrophilic metal cations in synthetic macrocyclic hosts Van Staveren, Catherina J.; Van Eerden, Johan.; Van Veggel, Frank C. J. M. Journal of the American Chemical Society, Vol. 110, Issue 15 https://doi.org/10.1021/ja00223a017	journal	July 1988
Co-complexation of urea and UO22+ in a Schiff base macrocycle: a mimic of an enzyme binding site Van Staveren, Catherina J.; Fenton, David E.; Reinhoudt, David N. Journal of the American Chemical Society, Vol. 109, Issue 11 https://doi.org/10.1021/ja00245a045	journal	May 1987
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
The Effects of Redox-Inactive Metal Ions on the Activation of Dioxygen: Isolation and Characterization of a Heterobimetallic Complex Containing a Mn ^III –(μ-OH)–Ca ^II Core Park, Young Jun; Ziller, Joseph W.; Borovik, A. S. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja203458d	journal	June 2011
Assembly and Properties of Heterobimetallic Co ^II/III /Ca ^II Complexes with Aquo and Hydroxo Ligands Lacy, David C.; Park, Young Jun; Ziller, Joseph W. Journal of the American Chemical Society, Vol. 134, Issue 42 https://doi.org/10.1021/ja304525n	journal	October 2012
Efficient Catalytic Oxidation of Alkanes by Lewis Acid/[Os ^VI (N)Cl ₄ ] ⁻ Using Peroxides as Terminal Oxidants. Evidence for a Metal-Based Active Intermediate Yiu, Shek-Man; Man, Wai-Lun; Lau, Tai-Chu Journal of the American Chemical Society, Vol. 130, Issue 32 https://doi.org/10.1021/ja802625e	journal	August 2008
Uranyl to Uranium(IV) Conversion through Manipulation of Axial and Equatorial Ligands Bell, Nicola L.; Shaw, Brian; Arnold, Polly L. Journal of the American Chemical Society, Vol. 140, Issue 9 https://doi.org/10.1021/jacs.7b13474	journal	February 2018
Gas-Phase Energetics of Actinide Oxides: An Assessment of Neutral and Cationic Monoxides and Dioxides from Thorium to Curium ^† Marçalo, Joaquim; Gibson, John K. The Journal of Physical Chemistry A, Vol. 113, Issue 45 https://doi.org/10.1021/jp904862a	journal	November 2009
NMR Chemical Shifts of Trace Impurities: Common Laboratory Solvents, Organics, and Gases in Deuterated Solvents Relevant to the Organometallic Chemist Fulmer, Gregory R.; Miller, Alexander J. M.; Sherden, Nathaniel H. Organometallics, Vol. 29, Issue 9 https://doi.org/10.1021/om100106e	journal	May 2010
Reduction and selective oxo group silylation of the uranyl dication Arnold, Polly L.; Patel, Dipti; Wilson, Claire Nature, Vol. 451, Issue 7176 https://doi.org/10.1038/nature06467	journal	January 2008
Redox-inactive metals modulate the reduction potential in heterometallic manganese–oxido clusters Tsui, Emily Y.; Tran, Rosalie; Yano, Junko Nature Chemistry, Vol. 5, Issue 4 https://doi.org/10.1038/nchem.1578	journal	March 2013
Redox-inactive metal ions modulate the reactivity and oxygen release of mononuclear non-haem iron(III)–peroxo complexes Bang, Suhee; Lee, Yong-Min; Hong, Seungwoo Nature Chemistry, Vol. 6, Issue 10 https://doi.org/10.1038/nchem.2055	journal	September 2014
Crystal structure of a metal ion-bound oxoiron(IV) complex and implications for biological electron transfer Fukuzumi, Shunichi; Morimoto, Yuma; Kotani, Hiroaki Nature Chemistry, Vol. 2, Issue 9 https://doi.org/10.1038/nchem.731	journal	July 2010
Uranyl oxo activation and functionalization by metal cation coordination Arnold, Polly L.; Pécharman, Anne-Frédérique; Hollis, Emmalina Nature Chemistry, Vol. 2, Issue 12 https://doi.org/10.1038/nchem.904	journal	November 2010
Recent advances in cooperative bimetallic asymmetric catalysis: dinuclear Schiff base complexes Matsunaga, Shigeki; Shibasaki, Masakatsu Chem. Commun., Vol. 50, Issue 9 https://doi.org/10.1039/C3CC47587E	journal	January 2014
Catalytic one-electron reduction of uranyl( vi ) to Group 1 uranyl( v ) complexes via Al( iii ) coordination Zegke, Markus; Nichol, Gary S.; Arnold, Polly L. Chemical Communications, Vol. 51, Issue 27 https://doi.org/10.1039/C5CC00867K	journal	January 2015
Incorporation of redox-inactive cations promotes iron catalyzed aerobic C–H oxidation at mild potentials Chantarojsiri, Teera; Ziller, Joseph W.; Yang, Jenny Y. Chemical Science, Vol. 9, Issue 9 https://doi.org/10.1039/C7SC04486K	journal	January 2018
The effect of iron binding on uranyl( v ) stability Faizova, Radmila; White, Sarah; Scopelliti, Rosario Chemical Science, Vol. 9, Issue 38 https://doi.org/10.1039/C8SC02099J	journal	January 2018
Polydentate ligand exchange via formation of a dimetallic complex. Crystal structures of [(thf)Fe(acen)MCl ₂ ](M = Fe or Zn), [ClFe(salphen)FeCl(thf) ₂ ], [Ti(acen)(thf) ₂ ][CoCl ₃ (thf)], and [Ti(acen)(thf) ₂ ] ₂ [Fe ₃ Cl ₈ (thf) ₂ ][acen =N,N′-ethylenebis(acetylacetoneiminate), salphen =N,N′-o-phenylenebis(salicylideneiminate), and thf = tetrahydrofuran] Solari, Euro; Corazza, Fabio; Floriani, Carlo J. Chem. Soc., Dalton Trans., Issue 4 https://doi.org/10.1039/DT9900001345	journal	January 1990
Lewis acid-activated oxidation of alcohols by permanganate Du, Hongxia; Lo, Po-Kam; Hu, Zongmin Chemical Communications, Vol. 47, Issue 25 https://doi.org/10.1039/c1cc12024g	journal	January 2011
Multimetallic Schiff Base Complexes as Cooperative Asymmetric Catalysts Matsunaga, Shigeki; Shibasaki, Masakatsu Synthesis, Vol. 45, Issue 04 https://doi.org/10.1055/s-0032-1316846	journal	January 2013
A Synthetic Model of the Mn3Ca Subsite of the Oxygen-Evolving Complex in Photosystem II Kanady, J. S.; Tsui, E. Y.; Day, M. W. Science, Vol. 333, Issue 6043 https://doi.org/10.1126/science.1206036	journal	August 2011
NMR nomenclature. Nuclear spin properties and conventions for chemical shifts(IUPAC Recommendations 2001) Harris, Robin K.; Becker, Edwin D.; Cabral de Menezes, Sonia M. Pure and Applied Chemistry, Vol. 73, Issue 11 https://doi.org/10.1351/pac200173111795	journal	January 2001
Further conventions for NMR shielding and chemical shifts (IUPAC Recommendations 2008) Harris, Robin K.; Becker, Edwin D.; Cabral de Menezes, Sonia M. Pure and Applied Chemistry, Vol. 80, Issue 1 https://doi.org/10.1351/pac200880010059	journal	January 2008

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Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes

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