Review
Chemistry, Inorganic & Nuclear
Joy H. Farnaby, Tajrian Chowdhury, Samuel J. Horsewill, Bradley Wilson, Florian Jaroschik
Summary: This review summarizes the progress in organo-f-element chemistry in 2019, focusing on the discovery of new types of complexes, diverse reactivities of lanthanide metals, and reports on novel catalytic reactions. Advancements in hydrocarbyl complexes of the actinides are also highlighted.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Engineering, Chemical
Yimin Cai, Seraj A. Ansari, Lihua Yuan, Wen Feng, Prasanta K. Mohapatra
Summary: In this study, efficient actinide/lanthanide separation from acidic solutions was achieved using solvent extraction systems comprising different pillar[5]-arene-based picolinamide ligands with various substituted groups and the ionic liquid, C4mimNTf2. The extraction performance of the ligands was substantially changed by altering the pyridine nitrogen basicity through substitution of chlorine or methoxy groups. The extracted complexes were found to have a distorted structure with ligands directly coordinated to the metal ion, and the differences in extraction ability were attributed to variations in the bonding strength between pyridine nitrogens and metal ions.
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
(2023)
Article
Chemistry, Inorganic & Nuclear
Dennis A. Buschmann, David Schneider, Cacilia Maichle-Moessmer, Reiner Anwander
Summary: Diffusion of Me3SiI or direct addition of halogenating reagents can lead to the synthesis of lanthanide ring-clusters hybrids as well as different halogenated cluster systems, along with some byproducts.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Emily Y. Tsui, Keaton V. Prather
Summary: Irradiating cobalt metallocenes at specific energies causes the destabilization of the cyclopentadienyl-cobalt bond and the release of radicals. These radicals can be detected by EPR spectroscopy and chemically captured using hydrogen-atom-donating reagents. This reaction offers a new photochemical method for generating cobalt complexes or catalytic cyclopentadienyl cobalt(I) species for [2 + 2 + 2] cyclotrimerization reactions. Additionally, the results highlight that cobaltocene is not a photostable redox reagent under various conditions, including those relevant to photovoltaics or photocatalysis.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Attila Kovacs, Christos Apostolidis, Olaf Walter
Summary: The structures and bonding properties of 16 complexes formed by trivalent f elements with cyclopentadienyl and cyclohexylisonitrile ligands were studied, and the interactions between actinides and lanthanides were compared. The results show that the anionic Cp and neutral C equivalent to NCy ligands have comparable interactions with the metals in the complexes, and there are small but characteristic differences between actinide and lanthanide complexes.
Review
Chemistry, Multidisciplinary
Lisa Wirtz, Andre Schafer
Summary: Metallocenes with interlinked cyclopentadienide ligands, also known as ansa-metallocenes or metallocenophanes, can have drastically different properties than their unbridged parent compounds. This concept is not limited to transition metals, but can also be applied to many main-group elements. This review focuses on recent advances in synthesis, structure, and properties of metallocenophanes based on group 2, group 13, group 14, and group 15 main-group elements.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Review
Biochemistry & Molecular Biology
Qin Wang, Ziyi Liu, Yu-Fei Song, Dongqi Wang
Summary: In order to better understand the mechanism of liquid-liquid extraction, this study discusses the contributing factors for extraction (specifically, the sulfur-donating ligand, Cyanex301) through molecular dynamics simulations and experiments. This work is expected to contribute to our systematic understanding on a molecular scale of lanthanides and actinides extraction and assist in the extensive studies on the design and optimization of novel ligands with improved performance.
Article
Multidisciplinary Sciences
Zhipeng Wang, Liqin Huang, Xue Dong, Tong Wu, Qi Qing, Jing Chen, Yuexiang Lu, Chao Xu
Summary: An efficient separation strategy based on ion sieving in graphene oxide membrane is reported for the separation of actinides from lanthanides. This work realizes the group separation of actinides from lanthanides under highly acidic conditions by a simple ion sieving strategy and highlights the great potential of utilizing graphene oxide membrane for nuclear waste treatment.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Sudip Baguli, Sumana Mondal, Chhotan Mandal, Santu Goswami, Debabrata Mukherjee
Summary: This article provides an overview of the impact of electron-rich cyclopentadienyl and analogous ligands in stabilizing electron-deficient metal centers, particularly alkaline earth metals. It highlights the systematic variation of these compounds from beryllium to barium.
CHEMISTRY-AN ASIAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Lei Xu, Yuxun Hao, Xiao Yang, Zhipeng Wang, Chao Xu, Nataliya E. Borisova, Mingze Sun, Xingwang Zhang, Lecheng Lei, Chengliang Xiao
Summary: Two new phosphine oxide-functionalized 1,10-phenanthroline ligands, L-1 and L-2, were synthesized and studied for their coordination with trivalent actinides and lanthanides. Different complexation mechanisms and stability constants were elucidated using various analytical methods. L-1 exhibited strong extraction ability for Am-III and Eu-III, while L-2 showed minimal extraction due to its high hydrophilicity. The structures and bonding natures of the formed complex species were analyzed using DFT calculations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Engineering, Environmental
Jenny Jessat, Henry Moll, Warren A. John, Marie -Louise Bilke, Rene Hubner, Jerome Kretzschmar, Robin Steudtner, Bjorn Drobot, Thorsten Stumpf, Susanne Sachs
Summary: Daucus carota suspension cells exhibit a high affinity towards Eu(III) and U(VI) and interact with them through a bio-association process. The uptake of U(VI) involves the Ca ion channels and leads to bioprecipitation in the vacuole. Local concentration of Eu(III) is observed in the cell wall and cytoplasm, co-localized with phosphorous and oxygen.
JOURNAL OF HAZARDOUS MATERIALS
(2022)
Article
Chemistry, Inorganic & Nuclear
Petr Matveev, Pin-Wen Huang, Anna A. Kirsanova, Ivan Ananyev, Tsagana B. Sumyanova, Anastasia Kharcheva, Evgenii Yu Khvorostinin, Vladimir G. Petrov, Wei-Qun Shi, Stepan N. Kalmykov, Nataliya E. Borisova
Summary: Hybrid donor extractants based on sterically loaded diphosphonate ligands showed promising efficiency and selectivity in separating trivalent actinides and lanthanides. Among the studied ligands, phenanthroline-based extractants exhibited the highest efficiency in extracting Am(III) from nitric acid solutions, forming complexes with high quantum yields. X-ray diffraction studies revealed closer contacts of f-elements with aromatic N atoms in sterically loaded P = O ligands compared to sterically deficient ligands, providing insights into the observed selectivity trends.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
L. Havela
Summary: This paper provides a brief overview of the impact of hydrogen presence in metallic systems on magnetic properties, emphasizing the differences between different systems and using materials with similar crystal structures for comparison. The analysis is based on general aspects of hydrogen bonding in a metallic environment, hydrogen expanding volume, and polar bonding of hydrogen. Electronegativity is used as a convenient indicator quantifying the polar bonding character.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Chemistry, Inorganic & Nuclear
Chao Xu, Tingting Liu, Qian Liu, Suliang Yang, Dingming Li, Guoxin Tian
Summary: The similarity of coordination chemistry between Am(III) and Eu(III) and two homologous tridentate ligands, DEHAPA and DMAPA, was revealed through structural and spectroscopic analysis of complexes ML'(3) (org), ML3 (aq), and ML3 (s).
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Zhipeng Wang, Jun-Bo Lu, Xue Dong, Qiang Yan, Xiaogui Feng, Han-Shi Hu, Shuao Wang, Jing Chen, Jun Li, Chao Xu
Summary: Lanthanide/actinide separation is a worldwide challenge for atomic energy and nuclear waste treatment. This study presents a novel strategy to generate stable pentavalent Am (Am(V)) through coordination of Am(III) with a diglycolamide ligand and oxidation with Bi(V) species in the presence of an organic solvent. This strategy enables efficient stabilization of Am(V) and an extraordinarily high separation factor (>104) of Am from Ln, providing a new avenue for the high-OS chemistry of Am and fulfilling the crucial task of Ln/Am separation in the nuclear fuel cycle.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Conrad A. P. Goodwin, Sierra R. Ciccone, Samuel Bekoe, Sourav Majumdar, Brian L. Scott, Joseph W. Ziller, Andrew J. Gaunt, Filipp Furche, William J. Evans
Summary: New coordination environments for Np(III) and Pu(III) are reported based on pilot studies, with U(III) also studied in the same context. Complexes obtained through reactions showed different electron configurations for U(III), Np(III), and Pu(III).
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Justin C. Wedal, Joseph W. Ziller, Filipp Furche, William J. Evans
Summary: Heteroleptic U(III) complexes supported by bis(cyclopentadienyl) frameworks were synthesized and evaluated as precursors to U(II) complexes. The complexes were compared with other related compounds, and their electrochemical behavior was studied, revealing redox couples for U(IV)/U(III) and U(III)/U(II) transitions. The targeted U(II) complexes were analyzed using density functional theory, showing a 5f(3)6d(1) electron configuration as the ground state in each case.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Krishnendu Kundu, Jessica R. K. White, Samuel A. Moehring, Jason M. Yu, Joseph W. Ziller, Filipp Furche, William J. Evans, Stephen Hill
Summary: By controlling the degree of s-orbital mixing in molecules, a large spin hyperfine interaction can be achieved, leading to a 9 GHz clock transition and increased phase memory time. These findings suggest new strategies for the development of molecular quantum technologies.
Article
Chemistry, Inorganic & Nuclear
Justin C. Wedal, Joseph W. Ziller, William J. Evans
Summary: This study found that 1,3,5-trimethyltriazacyclohexane readily adds to bismuth triiodide to form various coordination compounds with different structures and properties, depending on the stoichiometry, solvent, and crystallization conditions.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Lauren M. Anderson-Sanchez, Jason M. Yu, Joseph W. Ziller, Filipp Furche, William J. Evans
Summary: The sterically bulky aryloxide ligand OAr* has been used to synthesize thermally stable Ln(II) complexes across the lanthanide series. Reduction of Ln(III) precursors Ln(OAr*)3 with potassium graphite and 2.2.2-cryptand yielded the Ln(II) complexes. The La and Ce complexes were challenging to isolate but could be obtained with the use of 18-crown-6 as a potassium chelator.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Justin C. Wedal, Jesse Murillo, Joseph W. Ziller, Brian L. Scott, Andrew J. Gaunt, William J. Evans
Summary: Me3tach readily complexes uranium triiodide to form (Me3tach)2UI3, which is soluble in THF and arenes and can serve as a source of UI3 to form organometallic U(III) complexes. When dissolved in pyridine, (Me3tach)2UI3 forms (Me3tach)UI3(py)2. A comparison was made with a related complex (Me3tacn)UI3(THF) using the larger ligand Me3tacn. Neptunium and plutonium complexes (Me3tach)2NpI3 and (Me3tach)2PuI3 were synthesized in a similar manner.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Amanda B. Chung, Cary R. Stennett, William N. G. Moore, Ming Fang, Joseph W. Ziller, William J. Evans
Summary: The reduction of tris(amide) complexes Ln(NR2)3 (R = SiMe3) with potassium graphite in the presence of various ethers demonstrates high reactivity, as shown by crystal structures of different C-O bond cleavage reactions. The study also highlights the diverse reaction pathways and difficulties in isolating Ln(II) complexes containing the [Ln(NR2)3]1- anion.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Cary R. Stennett, Joseph Q. Nguyen, Joseph W. Ziller, William J. Evans
Summary: The feasibility of using redox-active 2,2'-bipyridine as an electron carrier for lanthanide metallocenes was examined. The synthesis and characterization of Cp*2LnCl-(bipy) and Cp*2Ln(bipy) complexes were carried out. The complexes were then used to achieve two-electron reduction chemistry, including the reduction of azobenzene and the formation of lanthanide organometallic complexes with a (S5)2- ligand.
Article
Nanoscience & Nanotechnology
William N. G. Moore, Timothy J. McSorley, Alexandre Vincent, Joseph W. Ziller, Luis A. Jauregui, William J. Evans
Summary: The utility of molecular precursors for constructing van der Waals heterostructures was explored by studying the compound [(THF)Cs(mu- eta 5:eta 5-Cp ')3TmII]. Thin films were successfully exfoliated from single crystals and stacked under hexagonal boron nitride to create an air-stable van der Waals heterostructure.
ACS APPLIED NANO MATERIALS
(2023)
Editorial Material
Public, Environmental & Occupational Health
Amanda B. B. Chung, Cy H. Fujimoto, William J. Evans
Summary: We present a narrative of an incident in a chemistry laboratory involving the purification of benzene using a distillation apparatus. The incident resulted in an injury to a graduate student and a fire causing $3.5 million in damages. Unfortunately, due to the extent of the fire, the direct cause of the incident could not be determined. Lessons learned from this incident include conducting risk assessments, maintaining proper lab housekeeping, updating chemical inventory, monitoring long duration experiments, calling for backup, ensuring compliance with building codes, wearing personal protective equipment, and always calling 911 during emergencies.
ACS CHEMICAL HEALTH & SAFETY
(2023)
Article
Chemistry, Inorganic & Nuclear
Cory J. Windorff, Conrad A. P. Goodwin, Joseph M. Sperling, Thomas E. Albrecht-Schonzart, Zhuanling Bai, William J. Evans, Zachary K. Huffman, Renaud Jeannin, Brian N. Long, David P. Mills, Todd N. Poe, Joseph W. Ziller
Summary: This study aimed to find a trivalent plutonium halide phosphine oxide compound but accidentally isolated a tetravalent plutonium halide compound, which was characterized using various techniques. A putative plutonyl complex was also observed, and a series of similar compounds were synthesized for comparison.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Joseph Q. Nguyen, Lauren M. Anderson-Sanchez, William N. G. Moore, Joseph W. Ziller, Filipp Furche, William J. Evans
Summary: The importance of the specific trialkylsilyl substituent in the cyclopentadienyl chemistry of C5H4SiR3 ligands has been demonstrated by the synthesis of low oxidation-state thorium complexes. Crystalline tris(monosilyl-substituted cyclopentadienyl) Th(III) and Th(II) complexes can be isolated when the substituent is isopropyl.
Article
Chemistry, Inorganic & Nuclear
Justin C. Wedal, Joseph W. Ziller, William J. Evans
Summary: The reactions of 1,3,5-trimethyl-triazacyclohexane with rare-earth metal iodide, chloride, and triflate salts were investigated as alternative precursors for THF-free reactions. These reactions produced soluble (Me(3)tach)(2)LnI(3) and (Me(3)tach)(2)LnCl3 complexes with unique structures.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Justin C. Wedal, Joseph W. Ziller, William J. Evans
Summary: In this study, the U(v) imido complex 1 was observed for the first time by crystallography, providing new insights into the reaction mechanisms of U(III) compounds with azide reagents.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Justin C. Wedal, Nathalia Cajiao, Michael L. Neidig, William J. Evans
Summary: A new synthesis of Th(ii) complexes has been discovered, which involves the addition of simple MX salts to Cp'' Th-3(III) in the presence of 18-crown-6 or 2.2.2-cryptand. This synthesis method is applicable to MX salts where M is Li, Na, K and X is H, Cl, Me, N-3.
CHEMICAL COMMUNICATIONS
(2022)