Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

Niklas, Julie E.; Hunter, Katherine M.; Gorden, Anne E. V.

doi:10.1021/acs.inorgchem.9b01695

Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

Journal Article · Tue Nov 05 00:00:00 EST 2019 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.9b01695· OSTI ID:1573133

Niklas, Julie E. ^[1]; Hunter, Katherine M. ^[2]; ^[2]

Auburn Univ., Auburn, AL (United States); Auburn University
Auburn Univ., Auburn, AL (United States)

Uranyl complexes of aryl-substituted α-diimine ligands gbha (UO₂-1a-f and phen-BIAN (UO₂-2a-f) (gbha (1) = glyoxal bis(2-hydroxyanil); phen-BIAN (2) = N,N'-bis-(iminophenol)acenaphthene; R = OMe (a), t-bu (b), H (c), Me (d), F (e), and naphthyl (f)) were designed, prepared, and characterized by X-ray diffraction, FT-IR, NMR, UV-Vis, and electrochemical methods. Furthermore these ligand frameworks contain a salen-type O-N-N-O binding pocket, but are redox-non-innocent, leading to unusual metal complex behaviors. Here, we describe three solid-state structures of uranyl complexes UO₂-1b, UO₂-1c, and UO₂-1f, and observe manifestations of ligand non-innocence for the U(VI) complexes UO₂-1b and UO₂-1c. The impacts of accessible π-systems and ligand substitution on the axial uranium-oxo interactions can be evaluated spectroscopically via the intraligand charge-transfer (ILCT) processes that dominate the absorption spectra of these complexes and through changes to the asymmetric (ν₃) O=U=O stretching frequency. This, in combination with electrochemical data, reveals the effects of the inclusion of the conjugated acenaphthene backbone and the importance of ligand electronic structure on uranyl’s bonding interactions.

View Accepted Manuscript (DOE)

Research Organization:: Auburn Univ., Auburn, AL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0019177

OSTI ID:: 1573133

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 22 Vol. 58; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

Four-Step Reduction of dpp-bian with Sodium Metal: Crystal Structures of the Sodium Salts of the Mono-, Di-, Tri- and Tetraanions of dpp-bian Fedushkin, Igor L.; Skatova, Alexandra A.; Chudakova, Valentina A. Angewandte Chemie International Edition, Vol. 42, Issue 28 https://doi.org/10.1002/anie.200351408	journal	July 2003
Synthese Makromolekularer Komplexbildner aus Aminophenolen und Glyoxal Bayer, Ernst Chemische Berichte, Vol. 90, Issue 12 https://doi.org/10.1002/cber.19570901212	journal	December 1957
The condensation product of 2-aminophenol and glyoxal. Structure and photochemistry Tauer, Erich; Grellmann, Karl-Heinz; Kaufmann, Eckhard Chemische Berichte, Vol. 119, Issue 11 https://doi.org/10.1002/cber.19861191111	journal	November 1986
Easy Entry into Reduced Ar-BIANH ₂ Compounds: A New Class of Quinone/Hydroquinone-Type Redox-Active Couples with an Easily Tunable Potential Viganò, Marta; Ferretti, Francesco; Caselli, Alessandro Chemistry - A European Journal, Vol. 20, Issue 44 https://doi.org/10.1002/chem.201403594	journal	September 2014
Reduction of 1,2-Bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-bian) with Alkali Metals− A Study of the Solution Behaviour of (dpp-bian)n−[M+]n (M = Li, Na;n = 1−4) with UV/Vis, ESR and1H NMR Spectroscopy Fedushkin, Igor L.; Skatova, Alexandra A.; Chudakova, Valentina A. European Journal of Inorganic Chemistry, Vol. 2004, Issue 2 https://doi.org/10.1002/ejic.200300351	journal	January 2004
Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms: Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interaction Kalaj, Mark; Carter, Korey P.; Cahill, Christopher L. European Journal of Inorganic Chemistry, Vol. 2017, Issue 40 https://doi.org/10.1002/ejic.201700788	journal	September 2017
Synthesis, UV-Vis and CV properties of a structurally related series of bis(Arylimino)acenaphthenes (Ar-BIANs): SYNTHESIS AND CHARACTERIZATION OF BIS(ARYLIMINO)ACENAPHTHENES (Ar-BIANs) Hasan, Kamrul; Zysman-Colman, Eli Journal of Physical Organic Chemistry, Vol. 26, Issue 3 https://doi.org/10.1002/poc.3081	journal	January 2013
Novel homogeneous Salen Mn(III) catalysts synthesized from dialdehyde or diketone with o-aminophenol for catalyzing epoxidation of alkenes Xiong, Donglu; Fu, Zaihui; Zhong, Sheng Catalysis Letters, Vol. 113, Issue 3-4 https://doi.org/10.1007/s10562-007-9018-8	journal	February 2007
An analysis of the bonding in some ‘nonclassical’ d0 and d10 metal carbonyl complexes Lynn, Matthew A.; Bursten, Bruce E. Inorganica Chimica Acta, Vol. 229, Issue 1-2 https://doi.org/10.1016/0020-1693(94)04278-4	journal	February 1995
Systematics in the vibrational spectra of uranyl complexes Jones, Llewellyn H. Spectrochimica Acta, Vol. 10, Issue 4 https://doi.org/10.1016/0371-1951(58)80107-1	journal	February 1958
Spectroscopic and theoretical investigations of Schiff base metal complexes with intraligand charge-transfer behavior Benedix, Roland; Dietz, Fritz; Hennig, Horst Inorganica Chimica Acta, Vol. 147, Issue 2 https://doi.org/10.1016/S0020-1693(00)83368-X	journal	July 1988
Oxo ligand functionalization in the uranyl ion (UO22+) Fortier, Skye; Hayton, Trevor W. Coordination Chemistry Reviews, Vol. 254, Issue 3-4 https://doi.org/10.1016/j.ccr.2009.06.003	journal	February 2010
Colorimetric determination of calcium using reagents of the glyoxal bis(2-hydroxyanil) class Milligan, Carl W.; Lindstrom, Frederick. Analytical Chemistry, Vol. 44, Issue 11 https://doi.org/10.1021/ac60319a019	journal	September 1972
Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion Arnold, Polly L.; Pécharman, Anne-Frédérique; Lord, Rianne M. Inorganic Chemistry, Vol. 54, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b00420	journal	March 2015
Oxo Ligand Substitution in a Cationic Uranyl Complex: Synergistic Interaction of an Electrophile and a Reductant Pedrick, Elizabeth A.; Wu, Guang; Hayton, Trevor W. Inorganic Chemistry, Vol. 54, Issue 14 https://doi.org/10.1021/acs.inorgchem.5b01077	journal	July 2015
U–O _yl Stretching Vibrations as a Quantitative Measure of the Equatorial Bond Covalency in Uranyl Complexes: A Quantum-Chemical Investigation Di Pietro, Poppy; Kerridge, Andrew Inorganic Chemistry, Vol. 55, Issue 2 https://doi.org/10.1021/acs.inorgchem.5b01219	journal	November 2015
Perturbation of the O–U–O Angle in Uranyl by Coordination to a 12-Membered Macrocycle Pedrick, Elizabeth A.; Schultz, Jason W.; Wu, Guang Inorganic Chemistry, Vol. 55, Issue 11 https://doi.org/10.1021/acs.inorgchem.6b00799	journal	May 2016
Redox-Active vs Redox-Innocent: A Comparison of Uranium Complexes Containing Diamine Ligands Pattenaude, Scott A.; Mullane, Kimberly C.; Schelter, Eric J. Inorganic Chemistry, Vol. 57, Issue 11 https://doi.org/10.1021/acs.inorgchem.8b00663	journal	May 2018
Structural Characterization and Redox Activity of a Uranyl Dimer and Transition-Metal Complexes of a Tetradentate BIAN Ligand Niklas, Julie E.; Farnum, Byron H.; Gorden, John D. Organometallics, Vol. 36, Issue 23 https://doi.org/10.1021/acs.organomet.7b00454	journal	August 2017
The Chemistry of Stable Phenoxy Radicals Altwicker, Elmer R. Chemical Reviews, Vol. 67, Issue 5 https://doi.org/10.1021/cr60249a001	journal	October 1967
Bioreduction of Uranium: Environmental Implications of a Pentavalent Intermediate Renshaw, Joanna C.; Butchins, Laura J. C.; Livens, Francis R. Environmental Science & Technology, Vol. 39, Issue 15 https://doi.org/10.1021/es048232b	journal	August 2005
Paramagnetic Bis(1,4-di-tert-butyl-1,4-diazabutadiene) Adducts of Lithium, Magnesium, and Zinc Gardiner, Michael G.; Hanson, Graeme R.; Henderson, Mark J. Inorganic Chemistry, Vol. 33, Issue 11 https://doi.org/10.1021/ic00089a024	journal	May 1994
Tetradentate Bis( o -iminobenzosemiquinonate(1−)) π Radical Ligands and Their o -Aminophenolate(1−) Derivatives in Complexes of Nickel(II), Palladium(II), and Copper(II) Min, Kil Sik; Weyhermüller, Thomas; Bothe, Eberhard Inorganic Chemistry, Vol. 43, Issue 9 https://doi.org/10.1021/ic0302480	journal	May 2004
Synthesis, Characterization, and Multielectron Reduction Chemistry of Uranium Supported by Redox-Active α-Diimine Ligands Kraft, Steven J.; Williams, Ursula J.; Daly, Scott R. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2002805	journal	October 2011
Computational Insights into Uranium Complexes Supported by Redox-Active α-Diimine Ligands Li Manni, Giovanni; Walensky, Justin R.; Kraft, Steven J. Inorganic Chemistry, Vol. 51, Issue 4 https://doi.org/10.1021/ic202522w	journal	January 2012
Experimental and Theoretical Approaches to Redox Innocence of Ligands in Uranyl Complexes: What Is Formal Oxidation State of Uranium in Reductant of Uranyl(VI)? Takao, Koichiro; Tsushima, Satoru; Ogura, Toshinari Inorganic Chemistry, Vol. 53, Issue 11 https://doi.org/10.1021/ic5006314	journal	May 2014
Bent cis d0 MoO22+ vs. linear trans d0f0 UO22+: a significant role for nonvalence 6p orbitals in uranyl Tatsumi, Kazuyuki; Hoffmann, Roald Inorganic Chemistry, Vol. 19, Issue 9 https://doi.org/10.1021/ic50211a035	journal	September 1980
The Monoanionic π-Radical Redox State of α-Iminoketones in Bis(ligand)metal Complexes of Nickel and Cobalt Lu, Connie C.; Bill, Eckhard; Weyhermüller, Thomas Inorganic Chemistry, Vol. 46, Issue 19 https://doi.org/10.1021/ic7008094	journal	September 2007
Noninnocence of the Ligand Glyoxal-bis(2-mercaptoanil). The Electronic Structures of [Fe(gma)] ₂ , [Fe(gma)(py)]·py, [Fe(gma)(CN)] ¹ ^- ^/0 , [Fe(gma)I], and [Fe(gma)(PR ₃ ) _n ] ( n = 1, 2). Experimental and Theoretical Evidence for “Excited State” Coordination Ghosh, Prasanta; Bill, Eckhard; Weyhermüller, Thomas Journal of the American Chemical Society, Vol. 125, Issue 5 https://doi.org/10.1021/ja021123h	journal	February 2003
Synthesis, Characterization, and Reactivity of a Uranyl β-Diketiminate Complex Hayton, Trevor W.; Wu, Guang Journal of the American Chemical Society, Vol. 130, Issue 6 https://doi.org/10.1021/ja077538q	journal	February 2008
High-Valent Uranium Alkyls: Evidence for the Formation of U ^VI (CH ₂ SiMe ₃ ) ₆ Fortier, Skye; Walensky, Justin R.; Wu, Guang Journal of the American Chemical Society, Vol. 133, Issue 30 https://doi.org/10.1021/ja204151v	journal	August 2011
Oxo-Functionalization and Reduction of the Uranyl Ion through Lanthanide-Element Bond Homolysis: Synthetic, Structural, and Bonding Analysis of a Series of Singly Reduced Uranyl–Rare Earth 5f ¹ -4f ⁿ Complexes Arnold, Polly L.; Hollis, Emmalina; Nichol, Gary S. Journal of the American Chemical Society, Vol. 135, Issue 10 https://doi.org/10.1021/ja308993g	journal	March 2013
Investigation of the Electronic Ground States for a Reduced Pyridine(diimine) Uranium Series: Evidence for a Ligand Tetraanion Stabilized by a Uranium Dimer Anderson, Nickolas H.; Odoh, Samuel O.; Williams, Ursula J. Journal of the American Chemical Society, Vol. 137, Issue 14 https://doi.org/10.1021/ja511867a	journal	April 2015
Reduced Uranium Complexes: Synthetic and DFT Study of the Role of π Ligation in the Stabilization of Uranium Species in a Formal Low-Valent State Korobkov, Ilia; Gorelsky, Serge; Gambarotta, Sandro Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja9002525	journal	July 2009
Synthesis, Characterization, and Stoichiometric U–O Bond Scission in Uranyl Species Supported by Pyridine(diimine) Ligand Radicals Kiernicki, John J.; Cladis, Dennis P.; Fanwick, Phillip E. Journal of the American Chemical Society, Vol. 137, Issue 34 https://doi.org/10.1021/jacs.5b06217	journal	August 2015
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
Electronic Structure and Bonding in Actinyl Ions and their Analogs Denning, Robert G. The Journal of Physical Chemistry A, Vol. 111, Issue 20 https://doi.org/10.1021/jp071061n	journal	May 2007
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
The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes Gregson, Matthew; Lu, Erli; Mills, David P. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14137	journal	February 2017
Back-bonding between an electron-poor, high-oxidation-state metal and poor π-acceptor ligand in a uranium(v)–dinitrogen complex Lu, Erli; Atkinson, Benjamin E.; Wooles, Ashley J. Nature Chemistry, Vol. 11, Issue 9 https://doi.org/10.1038/s41557-019-0306-x	journal	August 2019
A survey of pendant donor-functionalised (N,O) phosphine ligands for Cr-catalysed ethylene tri- and tetramerisation Suttil, James A.; Wasserscheid, Peter; McGuinness, David S. Catal. Sci. Technol., Vol. 4, Issue 8 https://doi.org/10.1039/C4CY00457D	journal	January 2014
Assessing covalency in equatorial U–N bonds: density based measures of bonding in BTP and isoamethyrin complexes of uranyl Di Pietro, Poppy; Kerridge, Andrew Physical Chemistry Chemical Physics, Vol. 18, Issue 25 https://doi.org/10.1039/C6CP01273F	journal	January 2016
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
Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands Bell, Nicola L.; Arnold, Polly L.; Love, Jason B. Dalton Transactions, Vol. 45, Issue 40 https://doi.org/10.1039/C6DT01948J	journal	January 2016
Inner-sphere vs. outer-sphere reduction of uranyl supported by a redox-active, donor-expanded dipyrrin Pankhurst, James R.; Bell, Nicola L.; Zegke, Markus Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC02912D	journal	January 2017
An example of unusual pyridine donor Schiff base uranyl (UO ₂ ²⁺ ) complexes Hardy, E. E.; Wyss, K. M.; Eddy, M. A. Chemical Communications, Vol. 53, Issue 42 https://doi.org/10.1039/C7CC02747H	journal	January 2017
Tuning the overpotential of electrocatalytically active cyclopentadienylnickel complexes containing 1,4-diaza-1,3-butadienes (DAB) for proton reduction Sondermann, Christina; Ringenberg, Mark R. Dalton Transactions, Vol. 46, Issue 16 https://doi.org/10.1039/C7DT00960G	journal	January 2017
Double uranium oxo cations derived from uranyl by borane or silane reduction Cowie, Bradley E.; Nichol, Gary S.; Love, Jason B. Chemical Communications, Vol. 54, Issue 31 https://doi.org/10.1039/C8CC00341F	journal	January 2018
Solid-state structural elucidation and electrochemical analysis of uranyl naphthylsalophen Niklas, Julie E.; Hardy, Emily E.; Gorden, Anne E. V. Chemical Communications, Vol. 54, Issue 83 https://doi.org/10.1039/C8CC05242E	journal	January 2018
Preparation and crystal structure of aqua[bis(2-hydroxyphenylimino)-ethanato-OO′NN′-]dioxouranium Bandoli, Giuliano; Clemente, Dore A. J. Chem. Soc., Dalton Trans., Issue 7 https://doi.org/10.1039/DT9750000612	journal	January 1975
The use of glyoxal bis-(2-hydroxyanil) in determining microgram amounts of uranium Wilson, A. D. The Analyst, Vol. 87, Issue 1038 https://doi.org/10.1039/an9628700703	journal	January 1962
Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states Roy, Amit Saha; Muresan, Nicoleta; Tuononen, Heikki M. Dalton Transactions, Issue 26 https://doi.org/10.1039/b802063a	journal	January 2008
Infrared Spectra and Structure of Uranyl and Transuranium ( V ) and ( VI ) Ions in Aqueous Perchloric Acid Solution Jones, Llewellyn H.; Penneman, Robert A. The Journal of Chemical Physics, Vol. 21, Issue 3 https://doi.org/10.1063/1.1698941	journal	March 1953
The electronic structure of the uranyl ion: III. Theory Denning, R. G.; Snellgrove, T. R.; Woodwark, D. R. Molecular Physics, Vol. 37, Issue 4 https://doi.org/10.1080/00268977900100841	journal	April 1979
OLEX2 : a complete structure solution, refinement and analysis program Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J. Journal of Applied Crystallography, Vol. 42, Issue 2 https://doi.org/10.1107/S0021889808042726	journal	January 2009
A short history of SHELX Sheldrick, George M. Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122 https://doi.org/10.1107/S0108767307043930	journal	December 2007
Formation of New Tetradentate Schiff Base Metal Chelates Malek, Abdul; Fresco, James M. Canadian Journal of Chemistry, Vol. 51, Issue 12 https://doi.org/10.1139/v73-297	journal	June 1973

Similar Records

Tailoring Redox Active Ligands for Probing the Reactivity of Actinides

Technical Report · Wed Aug 31 00:00:00 EDT 2022 · OSTI ID:1899175

Reactivity of an aluminum hydride complex with a redox-active diimine ligand

Journal Article · Fri Dec 14 23:00:00 EST 2018 · Russian Chemical Bulletin · OSTI ID:22943339

Mononuclear gallium complexes with the redox-active dmp-bian ligand (dmp-bian is 1,2-bis[(2,6-dimethylphenyl)imino]acenaphthene): synthesis and reactions with alkynes

Journal Article · Thu Feb 14 23:00:00 EST 2019 · Russian Chemical Bulletin · OSTI ID:22943294

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
coordination
electrochemistry
uranium

CCDC 1918535: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22dd74 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918539: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddc8 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918540: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddd9 The current record is supplemented by this dataset	dataset	January 2019
CCDC 1918541: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22ddfb The current record is supplemented by this dataset	dataset	January 2019
CCDC 1921460: Experimental Crystal Structure Determination E., Niklas, Julie; M., Hunter, Katherine; V., Gorden, Anne E. https://doi.org/10.5517/ccdc.csd.cc22hflm The current record is supplemented by this dataset	dataset	January 2019

Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation

Citation Formats

References (57)

Linked Research (5)

Similar Records

Related Subjects