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

doi:10.1021/acs.inorgchem.9b01695

This content will become publicly available on November 5, 2020

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

Full Record
Other Related Research

Abstract

Uranyl complexes of aryl-substituted α-diimine ligands gbha (UO ₂-1a-f and phen-BIAN (UO ₂-2a-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 UO ₂-1b, UO ₂-1c, and UO ₂-1f, and observe manifestations of ligand non-innocence for the U(VI) complexes UO ₂-1b and UO ₂-1c. 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 (ν ₃) 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.

Authors:

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

^[1]

Auburn Univ., Auburn, AL (United States)

Publication Date:: 2019-11-05

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

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

OSTI Identifier:: 1573133

Grant/Contract Number:: SC0019177

Resource Type:: Accepted Manuscript

Journal Name:: Inorganic Chemistry

Additional Journal Information:: Journal Name: Inorganic Chemistry; Journal ID: ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; uranium; electrochemistry; coordination

Citation Formats


                    Niklas, Julie E., Hunter, Katherine M., and Gorden, Anne E. V. Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation.  United States: N. p., 2019. 
        Web.  doi:10.1021/acs.inorgchem.9b01695.

Copy to clipboard


                    Niklas, Julie E., Hunter, Katherine M., & Gorden, Anne E. V. Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation.  United States.  doi:10.1021/acs.inorgchem.9b01695.

Copy to clipboard


                    Niklas, Julie E., Hunter, Katherine M., and Gorden, Anne E. V. Tue .  
        "Bonding Interactions in Uranyl α-Diimine Complexes: A Spectroscopic and Electrochemical Study of the Impacts of Ligand Electronics and Extended Conjugation".  United States.  doi:10.1021/acs.inorgchem.9b01695.

Copy to clipboard


                    
@article{osti_1573133,

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

  author       = {Niklas, Julie E. and Hunter, Katherine M. and Gorden, Anne E. V.},

  abstractNote = {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.},

  doi          = {10.1021/acs.inorgchem.9b01695},

  journal      = {Inorganic Chemistry},

  number       = ,

  volume       = ,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

This content will become publicly available on November 5, 2020

Publisher's Version of Record

DOI: 10.1021/acs.inorgchem.9b01695

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

Ruthenium Bis-diimine Complexes with a Chelating Thioether Ligand: Delineating 1,10-Phenanthrolinyl and 2,2'-Bipyridyl Ligand Substituent Effects

Journal Article Al-Rawashdeh, Nathir A. F. ; Chatterjee, Sayandev ; Krause, Jeanette A. ; ... - Inorganic Chemistry

A new series of ruthenium(II) bis-diimine complexes with a chelating thioether donor ligand has been prepared: Ru(diimine)2(dpte)2+ (diimine=1,10-phenanthroline (phen) (1); 5-CH3-phen (2), 5-Cl-phen (3); 5-Br-phen (4); 5-NO2-phen (5); 3,4,7,8-tetramethyl-phen (6); 4,7-diphenyl-phen (7); 5,5'-dimethyl-2,2'-bipyridine (8); 4,4'-di-tert-butyl-2,2'-bipyridine (9)). Crystal structures of 2, 5, 7 and 9 show that the complexes form 2 of the 12 possible conformational/configurational isomers, adopting compact C2-symmetric structures with short intramolecular transannular interactions between the diimine ligands and dpte phenyl groups; crystals of 2 and 5 contain non-statistical distributions of geometric isomers. In keeping with the π-acidity of the dpte, the Ru(III/II) couple, E°'(Ru3+/2+), occurs at relatively highmore »« less
DOI: 10.1021/ic4022454
Mononuclear, trinuclear, and hetero-trinuclear supramolecular complexes containing a new tri-sulfonate ligand and cobalt(II)/copper(II)-(1,10-phenanthroline){sub 2} building blocks

Journal Article Yu Yunfang ; Wei Yongqin ; Broer, Ria ; ... - Journal of Solid State Chemistry

Novel mononuclear, trinuclear, and hetero-trinuclear supermolecular complexes, [Co(phen){sub 2}(H{sub 2}O)(HTST)].2H{sub 2}O (1), [Co{sub 3}(phen){sub 6}(H{sub 2}O){sub 2}(TST){sub 2}].7H{sub 2}O (2), and [Co{sub 2}Cu(phen){sub 6}(H{sub 2}O){sub 2}(TST){sub 2}].10H{sub 2}O (3), have been synthesized by the reactions of a new tri-sulfonate ligand (2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, H{sub 3}TST) with the M{sup 2+} (M=Co, Cu) and the second ligand 1,10-phenanthroline (phen). Complex 1 contains a cis-Co(II)(phen){sub 2} building block and an HTST as monodentate ligand; complex 2 consists of two TST as bidentate ligands connecting one trans- and two cis-Co(II)(phen){sub 2} building blocks; complex 3 is formed by replacing the trans-Co(II)(phen){sub 2} in 2 with amore »« less
Luminescent hybrid lanthanide sulfates and lanthanide sulfonate-carboxylates with 1,10-phenanthroline involving in-situ oxidation of 2-mercaptonbenzoic acid

Journal Article Zhong, Jie-Cen ; Wan, Fang ; State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 ; ... - Journal of Solid State Chemistry

A series of lanthanide sulfates and lanthanide sulfonate-carboxylates, [Ln{sub 2}(phen){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O){sub 2}]{sub n} (I:Ln=Nd(1a), Sm(1b), Eu(1c), phen=1,10-phenanthroline) and [Ln(phen)(2-SBA)(BZA)]{sub n} (II: Ln=Sm(2a), Eu(2b), Dy(2c), 2-SBA=2-sulfobenzoate, BZA=benzoate) have been hydrothermally synthesized from lanthanide oxide, 2-mercaptonbenzoic acid with phen as auxiliary ligand and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra, TG analyses and luminescence spectroscopy. Interestingly, SO{sub 4}{sup 2−} anions in I came from the in situ deep oxidation of thiol groups of 2-mercaptonbenzoic acid while 2-sulfobenzoate and benzoate ligands in II from the middle oxidation and desulfuration reactions of 2-mercaptonbenzoic acid. Compounds I are organic–inorganic hybridmore »« less
DOI: 10.1016/J.JSSC.2014.08.037
Synthesis and characterization of molybdenum complexes containing diphosphine ligands of the type (ArCH{sub 2}){sub 2}PC{sub 2}H{sub 4}P(CH{sub 2}Ar){sub 2} (Ar = C{sub 6}H{sub 4}X). Electronic control of {eta}{sup 2}-dihydrogen versus dihydride coordination in MoH{sub 2}(CO)((RCH{sub 2}){sub 2}PC{sub 2}H{sub 4}P(CH{sub 2}R){sub 2}){sub 2} (R = Me, Pr{sup i}, C{sub 6}H{sub 4}X) and implications on the reaction coordinate for H{sub 2} cleavage

Journal Article Luo, Xiao-Liang ; Kubas, G.J. ; Burns, C.J. ; ... - Inorganic Chemistry

The bis(dinitrogen) molybdenum complexes trans-Mo(N{sub 2}){sub 2}((ArCH{sub 2}){sub 2}PC{sub 2}H{sub 4}P(CH{sub 2}Ar){sub 2}){sub 2} (Ar = C{sub 6}H{sub 5} (1a), C{sub 6}H{sub 4-} m-Me (1b), C{sub 6}H{sub 4}-o-Me (1c), C{sub 6}H{sub 4}-p-Me (1d), C{sub 6}H{sub 4}-o-F (1e), C{sub 6}H{sub 4}-m-F (1f) C{sub 6}H{sub 4}-p-F (1g), C{sub 6}H{sub 4}-m-OMe (1h), C{sub 6}H{sub 4}-p-OMe (1i)) are prepared by reduction of MoCl{sub 5} with magnesium under a dinitrogen atmosphere in the presence of the appropriate diphosphine ligand. Treatment of 1a and 1b with ethyl acetate in refluxing benzene under argon affords the formally 16-electron complexes MoCl{sub 5} with magnesium under a dinitrogen atmospheremore »« less
DOI: 10.1021/ic00101a013
Octahedral d[sup 6] Bis(maleimide) and Bis(maleic anhydride) complexes of molybdenum

Journal Article Lai, Chen-Hsing ; Cheng, Chien-Hong ; Liao, Fen-Ling ; ... - Inorganic Chemistry; (United States)

Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] reacts with 2 equiv of alkene, where the alkene is maleimide (MI), N-phenylmaleimide (PhMI), or N-methylmaleimide, to give the corresponding Mo(CO)[sub 2](alkene)[sub 2](CH[sub 3]CN)[sub 2] complex (1a-c, respectively) in excellent yield. Dissolution of 1 in DMSO led to the substitution of acetonitrile ligands by DMSO to form the corresponding cis bis(DMSO) complexes 2a-c. Addition of 1 equiv of NN to 1 yields MO(CO)[sub 2](alkene)[sub 2](alkene)[sub 2](NN) (NN = en, alkene = PhMI (3b), MeMI (3c); NN = o-phenylenediamine, alkene = PhMI (4)). Treatment of Mo-(CO)[sub 4](NN) (NN = phen or bpy), with 2 equiv of alkenemore »« less
DOI: 10.1021/ic00077a003

Similar Records