Article
Chemistry, Multidisciplinary
Quentin Le De, Amal Bouammali, Christian Bijani, Laure Vendier, Iker del Rosal, Dmitry A. Valyaev, Chiara Dinoi, Antoine Simonneau
Summary: By experiment and density functional theory (DFT), it is confirmed that the reported direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not exist. Instead, phenylithium reacts with one of the CO ligands to form an anionic acylcarbonyl dinitrogen metallate that decomposes to give a phenylate complex. The DFT calculations support the experimental results, and the direct attack of a nucleophile on metal-coordinated dinitrogen remains to be demonstrated.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Quinton J. Bruch, Santanu Malakar, Alan S. Goldman, Alexander J. M. Miller
Summary: This study demonstrates the electrochemical N-2 binding and splitting capabilities of a molybdenum complex, and investigates the reaction pathways and intermediates involved. Electrochemical kinetic analysis, spectroelectrochemical monitoring, and computational studies reveal two concurrent reaction pathways.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Botao Wu, Rui Feng, Zhu-Bao Yin, Haihan Yan, Xueli Wang, Gao-Xiang Wang, Junnian Wei, Zhenfeng Xi
Summary: This paper reported the synthesis, characterization, and theoretical studies of titanium-mu-N-2 complexes with di-anionic guanidinate ligands, which is the first example of its kind. The mono-anionic guanidinate-supported titanium-mu-N-2 complex 1 was obtained using (Me3Si)(2)N-guanidinate ligands. Reduction of 1 with potassium resulted in the formation of di-anionic guanidinate-supported titanium-mu-N-2 complex 2 by cleaving one N-Si bond of the (Me3Si)(2)N substituents in 1, changing the guanidinate ligands from mono-anionic to di-anionic and increasing the bond length of the mu-N-2 significantly. Characteristic studies and DFT calculations revealed that the di-anionic guanidinate ligands stabilized the geometry of 2 and increased the charge density on the bridging dinitrogen.
SCIENCE CHINA-CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Sai Manoj N. V. T. Gorantla, Kartik Chandra Mondal
Summary: The binding of dinitrogen to a sulfur-bridged Ni3S8 complex has been studied using density functional theory and energy decomposition analysis to understand the nature of the interaction and potential for hydrazine production in experimental conditions.
Article
Engineering, Electrical & Electronic
Thiago A. M. de Bairros, Pedro M. R. Pereira, Rausley A. A. de Souza, Michel D. Yacoub
Summary: In this correspondence, new fundamental statistics for the alpha-mu fading model are derived. These statistics include joint probability density functions, correlation coefficients, and power spectra for the fading model. An application example shows that assuming a uniform phase leads to a pessimistic scenario.
IEEE TRANSACTIONS ON VEHICULAR TECHNOLOGY
(2022)
Article
Chemistry, Multidisciplinary
Yixin Zhang, Jinfeng Zhao, Dawei Yang, Baomin Wang, Yuhan Zhou, Junhu Wang, Hui Chen, Tao Mei, Shengfa Ye, Jingping Qu
Summary: Researchers have discovered a well-described multi-iron nitrido model complex with excellent reactivity towards converting hydrogen and nitrogen gas into high-yield ammonia under ambient conditions. These studies have overcome the previous challenges of converting nitrides to ammonia and provided new insights.
Article
Chemistry, Applied
Akhil K. Sivan, Jisha Mary Thomas, Thayalaraj Christopher Jeyakumar, Chinnappan Sivasankar
Summary: Chemists have successfully used molybdenum bound nitrogen-doped graphene as a catalyst to activate and functionalise dinitrogen, achieving the goal of synthesising ammonia. The study also introduced the concept of FLP-H-2, which serves as a hydrogen source for the conversion.
APPLIED ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Zhen Pu, Jianwei Qin, Xiaoguo Fu, Ruizhi Qiu, Bin Su, Maobing Shuai, Fang Li
Summary: In this study, the structure and CO activation mechanism of mononuclear lanthanide (Ln) oxocarbonyl complexes OLn(12-CO) were investigated. It was found that the excitation of CO is related to the intramolecular charge transfer between the cationic LnO and CO, rather than the typically accepted metal-CO back-donation.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Jie Zeng, Rulin Qiu, Jun Zhu
Summary: Density functional theory (DFT) calculations are performed to screen experimentally viable FLPs for small-molecule activation, including N-2. Aromaticity is found to play an important role in most of these activations. The thermodynamic stabilities and low reaction barriers of the activation products could advance the development of FLP towards small-molecule activation, including N-2, and require experimental verification.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Zilong Zhao, Kaiyu Wang, Guoyuan Wu, Dengbang Jiang, Yaozhong Lan
Summary: The adsorption behavior of Sc on the surface of kaolinite (001) was studied using density functional theory. Hydrated Sc3+, ScOH2+, and ScOH2+ species had coordination numbers of eight, six, and five, respectively. The adsorption model was based on ScOH2H2O5+, which had the most stable ionic configuration in the liquid phase. Adsorption of Sc ionic species was categorized into outer layer and inner layer adsorptions based on adsorption energy and bonding mechanism. Hydrated Sc ions were mainly adsorbed on the outer layer of the kaolinite (001)Al-OH and (00-1)Si-O surfaces through hydrogen bonding, while also being adsorbed on the inner layer of the deprotonated kaolinite (001)Al-OH surface through coordination bonding.
Article
Thermodynamics
Tingting Jiao, Pengzheng Shi, Wenguang Du, Shoujun Liu, Shangguan Ju
Summary: The generation of N-2 during coal pyrolysis has the potential to reduce NOx emissions significantly. This paper investigates the effect of different active sites on N-2 production during coal pyrolysis using dinitrogen-containing model coals. The findings show that the different dinitrogen active sites mainly change the electronic properties of the carbonaceous surface, resulting in a slight difference in the energy barrier required for the fracture of the C-N bond.
COMBUSTION SCIENCE AND TECHNOLOGY
(2023)
Article
Chemistry, Physical
Ming Wang, Fei-Ying You, Min Gao, Zhi-Ying Chen, Lan-Ye Chu, Lian-Rui Hu, Jun Zhu, Jia-Bi Ma
Summary: This study reports the activation and coupling of N2 and O2 under thermochemical conditions at room temperature. The researchers found that Y2BO+ can react with one N2 and two O2 molecules, and detailed mechanistic studies were conducted using mass spectrometry and quantum chemical calculations.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Multidisciplinary
Samuel M. Bhutto, Reagan X. Hooper, Brandon Q. Mercado, Patrick L. Holland
Summary: This study reports a reaction sequence that activates C-H bonds in simple arenes and N-N triple bond in N2, allowing the formation of a new N-C bond and conversion of abundant feedstocks into N-containing organic compounds. The key step involves partial silylation of N2, followed by sequential silyl radical and silyl cation addition to form a kinetically competent iron(IV)-NN(SiMe3)2 intermediate that can be isolated at low temperature. This new pathway offers a method for functionalizing N2 using organometallic chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Pavel A. Shelyganov, Mehdi Elsayed Moussa, Michael Seidl, Manfred Scheer
Summary: The reactions between [Cp2Mo2(CO)(4)(mu,eta(2)-Sb-2)] (C) and Ag[TEF] in the presence of various N-donor ligands result in the selective formation of dimeric or tetrameric supramolecular coordination complexes and 1D or 2D coordination polymers. These compounds represent unique examples of supramolecular complexes incorporating both organometallic Sb-donor and organic N-donor ligands to stabilize metal ions. Notably, one of the formed compounds, the CP [Ag-4(eta(2 : 1)-C)(4)(L4)(4)](n)[TEF](4n), is an exceptional 1D polymer incorporating both N- and Sb-donor ligands as connectors for metal ions.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Mehdi Elsayed Moussa, Pavel A. Shelyganov, Michael Seidl, Eugenia Peresypkina, Nele Berg, Ruth M. Gschwind, Gabor Balazs, Jana Schiller, Manfred Scheer
Summary: The reaction of the organometallic diarsene complex with Ag[Al{OC(CF3)(3)}(4)] yielded the Ag-I monomer, which exhibits dynamic behavior in solution and allows the synthesis of organometallic-organic hybrid assemblies upon reaction with N-donor organic molecules. This stepwise pathway was supported by DFT calculations. The reaction with different organic molecules led to the formation of different types of molecular compounds and polymers, showcasing the potential for directed selective synthesis of complex structures.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
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, Multidisciplinary
Peng Zhang, Rizwan Nabi, Jakob K. Staab, Nicholas F. Chilton, Selvan Demir
Summary: We have synthesized two new sets of dibismuth-bridged rare earth molecules. The first series contains a bridging diamagnetic Bi22- anion while the second series comprises the first Bi23- radical-containing complexes for any d or f-block metal ions. The Bi23- radical-bridged terbium and dysprosium congeners are single-molecule magnets with magnetic hysteresis. These studies provide important insights into single-molecule magnetism, main group element, rare earth metal, and coordination chemistry.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(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
Francis Delano, Florian Benner, Seoyun Jang, Selvan Demir
Summary: In this study, three dinuclear rare earth complexes were synthesized through a protonolysis reaction and exhibited an unprecedented coordination mode for the pyrrolyl ligand. The complexes were characterized by crystallography, electrochemistry, and spectroscopy, and the Dy complex showed slow magnetic relaxation properties.
INORGANIC CHEMISTRY
(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
Florian Benner, Selvan Demir
Summary: The first use of the bare 2,2'-bisimidazole (H2bim) ligand in rare earth metal chemistry is reported, where a series of symmetric dinuclear complexes [(Cp*2RE)(2)(mu-bim)] were synthesized. These complexes were fully characterized and found to be redox-inactive. The Dy complex showed open magnetic hysteresis loops up to 5 K and slow magnetic relaxation up to 26 K, indicating potential applications in single-molecule magnets.
INORGANIC CHEMISTRY FRONTIERS
(2023)
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, Multidisciplinary
Florian Benner, Leo La Droitte, Olivier Cador, Boris Le Guennic, Selvan Demir
Summary: A judicious combination of radical ligands with paramagnetic metal ions elicits strong magnetic exchange coupling, which leads to important properties for future technologies. The metal-radical approach aids in effective magnetic communication, especially for lanthanide ions. The presented complexes of bisbenzimidazole-based dilanthanide exhibit strong antiferromagnetic coupling and single-molecule magnetism, showing potential for applications in organic radical bridge materials.
Article
Chemistry, Multidisciplinary
Rashmi Jena, Florian Benner, Francis Delano, Daniel Holmes, John McCracken, Selvan Demir, Aaron L. Odom
Summary: A room temperature stable complex, Y(NHAr*)(2), was prepared through KC8 reduction of ClY(NHAr*)(2), where Ar* = 2,6-(2,4,6-(Pr-i)(3)C6H2)C6H3. Through EPR evidence, it was shown that Y(NHAr*)(2) is a d(1) Y(ii) complex with significant delocalization of the unpaired electron density from the metal to the ligand. Interestingly, Y(NHAr*)(2) reacts as a radical donor towards (BuNC)-Bu-t, resulting in the formation of an unusual yttrium isocyanide complex, CNY(NHAr*)(2), as supported by spectroscopic evidence and single-crystal X-ray diffraction data.
Article
Chemistry, Multidisciplinary
Elizabeth R. Pugliese, Florian Benner, Selvan Demir
Summary: A rare organometallic yttrium bismuth cluster complex with a unique structure was isolated and characterized. The electronic structure of the complex was investigated using both experimental and computational methods.
CHEMICAL COMMUNICATIONS
(2023)
