Article
Chemistry, Multidisciplinary
Ilya P. Limarev, Genrikh E. Zelinskii, Svetlana A. Belova, Pavel Dorovatovskii, Anna V. Vologzhanina, Ekaterina G. Lebed, Yan Z. Voloshin
Summary: A comprehensive and straightforward synthetic strategy for iron(II) clathrochelates with functionalizing substituents has been developed. The reaction conditions and precursor-to-dinucleophile molar ratios play a crucial role in determining the number and characteristics of the substituents in the clathrochelates.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Samuel M. M. Bhutto, Brandon Q. Q. Mercado, Patrick L. L. Holland
Summary: In this study, the capability of iron(I) alkynyl complexes to bind N-2 was explored and a crystal structure of an iron(I) alkynyl complex with N-2 was obtained. It was further demonstrated that the alkynyl ligand is resistant to migration possibly due to the high Fe-C bond energy.
INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Inorganic & Nuclear
Matthew T. Whited
Summary: This Perspective summarizes the common modes of cooperativity demonstrated for pincer frameworks featuring metal/main-group bonds, highlighting similarities among boron, aluminium, and silicon donors and identifying directions for further development.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Physical
Sawako Yokota, Yuna Suzuki, Sachiko Yanagisawa, Takashi Ogura, Shunsuke Nozawa, Masahiko Hada, Hiroshi Fujii
Summary: This study successfully prepared and characterized bis-hypochlorite adducts of iron(III) porphyrin complexes, demonstrating that as the electron-donor effect of the ligands becomes stronger, the hypochlorite complex becomes more unstable and reactive. Additionally, spectroscopic studies and density functional theory calculations provided insights into the weakening Fe-OCl and O-Cl bonds in the iron-bound hypochlorite complex, leading to increased reactivity.
Article
Chemistry, Inorganic & Nuclear
Yanhong Dong, Shangqing Xie, Peng Zhang, Qingqing Fan, Xinyu Du, Hongjian Sun, Xiaoyan Li, Olaf Fuhr, Dieter Fenske
Summary: Six silyl cobalt(III) hydrides were synthesized with different substituents at the P and Si atoms, among which complex 3 exhibited excellent anti-Markovnikov regioselectivity as the best catalyst for alkene hydrosilylation. Addition of pyridine N-oxide reversed the selectivity of the reaction from anti-Markovnikov to Markovnikov addition, while maintaining high yield and excellent selectivity at a lower temperature. The proposed reaction mechanisms were based on experimental information, and the molecular structures of the complexes were determined by single crystal X-ray diffraction analysis.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yubin M. Kwon, Yuri Lee, Anna K. Schmautz, Timothy A. Jackson, Dong Wang
Summary: The recent focus on developing high-valent non-oxo-metal complexes has proven effective in studying their rich chemistry. In this study, a formal mononuclear Ni(IV)-nitrate complex was obtained and its geometric and electronic structures, bonding interactions, and spectroscopic properties were analyzed.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Inorganic & Nuclear
Williamson N. Oloo, Miklos Szavuly, Jozsef Kaizer, Lawrence Que
Summary: This study elucidates the substrate oxidations catalyzed by [Fe-II(IndH)(CH3CN)(3)](ClO4)(2) with H2O2, resulting in the formation of a spectroscopically characterized (mu-oxo)(mu-1,2-peroxo)diiron(III) intermediate capable of various oxidative reactions including epoxidation and hydroxylation.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Williamson N. Oloo, Miklos Szavuly, Jozsef Kaizer, Lawrence Que
Summary: This study describes a substrate oxidation reaction catalyzed by [Fe-II(IndH)(CH3CN)(3)](ClO4)(2) with H2O2, involving a spectroscopically characterized intermediate capable of olefin epoxidation and alkane hydroxylation. The research identified a direct nucleophilic attack of the substrate carbonyl group by the peroxo species. Additionally, the study found that the high-valent iron-oxo oxidant derived from O-O bond cleavage of the peroxo intermediate contributes to the oxidative reactivities associated with nonheme diiron enzymes.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Chuan-Kuei Chiang, Yu-Chiao Liu, Kai-Ti Chu, Jing-Ting Chen, Cheng-Yeh Tsai, Gene-Hsiang Lee, Ming-Hsi Chiang, Chien-Ming Lee
Summary: In this study, a dimeric and mononuclear Fe-NO model complex were synthesized and characterized, showing the formation of a thiolate-bridged bimetallic complex during the reduction of the mononuclear complex. The electronic structure of the bimetallic complex was described as a FeII/{Fe(NO)2}9 state, providing insights into the NO scrambling behavior in the activity of flavodiiron nitric oxide reductases (FNORs).
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Lindsey Paul, Melissa Gu, Sydney Moise, Daniel P. Harrison, Michael R. Norris
Summary: In this study, four Ru complexes containing bidentate polypyridyl ligands were synthesized. It was found that these complexes can selectively reduce CO2 to liquid fuels, with the involvement of amines playing a crucial role in this process.
ACS APPLIED ENERGY MATERIALS
(2022)
Article
Chemistry, Physical
Xiaodong Jin, Yongjie Lin, Robert P. Davies
Summary: This study investigates the intermediates and role of ancillary ligands in copper(I)-catalyzed intramolecular N-arylation reactions. Solid-state structures of copper(I) species with the reaction substrate and product are reported. In addition, kinetic profiling reveals negligible catalyst deactivation but significant catalyst inhibition. Based on these results, an improved catalytic protocol with sub-mol% catalyst loading has been developed.
CATALYSIS SCIENCE & TECHNOLOGY
(2023)
Article
Multidisciplinary Sciences
Li-Ping Xu, Shaoqun Qian, Zhe Zhuang, Jin-Quan Yu, Djamaladdin G. Musaev
Summary: This study investigates the mechanisms of palladium-catalyzed C-H lactonizations in aromatic carboxylic acids and explains the preference for functionalization of a C(sp3)-H bond. Understanding these mechanisms is important for expanding synthetic protocols and discovering more efficient and practical new C-H oxidation reactions.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Stephen N. N. Anderson, Josiah G. D. Elsberg, Lisa M. M. Berreau
Summary: Mononuclear bipyridine (bpy)-ligated Co(ii) chlorodiketonate complexes were synthesized and studied for O-2-dependent aliphatic C-C bond cleavage reactivity. The study found that illumination resulted in oxidative cleavage of the diketonate moiety, leading to the formation of several products.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Matthew J. G. Sinclair, Adrian B. Chaplin
Summary: A well-defined Pd(i) metalloradical reacts with aryl and alkyl iodides at room temperature, producing [Pd(PtBu3)(mu-I)](2) and phosphonium salts. Pd(ii) aryl/alkyl derivatives, indicating net radical oxidative addition, have been isolated and characterized crystallographically.
DALTON TRANSACTIONS
(2022)
Article
Mechanics
Bo Wang, Julien Rethore, Katerina E. Aifantis
Summary: This study investigates the stresses generated in a spherical particle during ion-insertion phase transformations. It highlights the effects of plastic deformation on diffusion-induced stresses and provides insights for designing mechanically stable phase transforming electrode materials.
INTERNATIONAL JOURNAL OF SOLIDS AND STRUCTURES
(2021)
Article
Engineering, Environmental
Sohan Lal, Richard J. Staples, Jean'ne M. Shreeve
Summary: New 1,1-diamino-2,2-dinitroethene (FOX-7)-based energetic salts were synthesized and characterized. The salts exhibited high density, good thermal stability and balanced nitrogen and oxygen contents. Their propulsive and detonation properties were evaluated and found to be superior to RDX and AP, and comparable to TKX-50. The energetic salts show potential as highly promising secondary explosives and solid propellants.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Austin L. Raithel, William E. Meador, Tea-Yon Kim, Richard J. Staples, Jared H. Delcamp, Thomas W. Hamann
Summary: Strong-field hexadentate ligands coordinated to cobalt metal centers resulted in three new low spin to low-spin Co(III/II) redox couples. The redox potential of the Co(III/II) redox couples could be tuned by modifying the ligand backbone with dimethyl amine groups. Despite the hexadentate ligands, the redox couples showed a reversible molecular switch rearrangement from five-coordinate Co(II) to six-coordinate Co(III).
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Review
Chemistry, Multidisciplinary
Efthalia Georgiou, Grigorios Raptopoulos, Ioannis Anastopoulos, Dimitrios A. Giannakoudakis, Michael Arkas, Patrina Paraskevopoulou, Ioannis Pashalidis
Summary: Aerogels are lightweight, nanoporous materials that have diverse applications and have been included in the top ten emerging technologies in chemistry for 2022. This review discusses the use of aerogel-based adsorbents for uranium removal and recovery and the factors affecting their adsorption efficiency and mechanism. The adsorbents show high sorption capacity for hexavalent uranium and follow Langmuir isotherm and pseudo-second-order kinetic models. Spectroscopic studies indicate the formation of inner-sphere complexes between surface active moieties and the uranyl cation. Aerogel-based adsorbents have potential in water treatment and uranium recovery, but further developments are needed to improve their selectivity for uranyl moieties.
Article
Crystallography
Brian Rawls, Jeremy Cunningham, John E. Bender, Richard J. Staples, Shannon M. Biros
Summary: The crystal structures of (Z)-(ethene-1,2-diyl)bis(diphenylphosphine sulfide) and its complex with Pt-II dichloride are described. Compound I features P = S bonds with a torsion angle between the two phosphine sulfide groups. The crystal structure of compound I exhibits both intramolecular C-H. . .S hydrogen bonds and pi-pi interactions. Compound II adopts a square-planar geometry. Molecules of compound II are linked by intermolecular C-H. . .Cl and C-H. . .S hydrogen bonds.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Suraj Kumar Sahoo, Brent Harfmann, Lin Ai, Qiuwen Wang, Sudip Mohapatra, Amitava Choudhury, Pericles Stavropoulos
Summary: A series of high-spin cationic M(II) sites (M = Mn, Fe, Co) supported by tripodal ( [N3N]) and bipodal ([N2N]) ligands featuring superbasic tetramethylguanidinyl residues have been synthesized. These catalysts can be used for the aziridination of olefins in acetonitrile solutions. In chlorinated solvents, the Fe(II) congeners are capable of mediating aziridine ring opening in situ followed by cycloaddition to afford five-membered N-heterocycles. The dicationic M(II) sites mediate nitrene-transfer reactions between imidoiodinane and styrenes to afford aziridines. The Fe(II) sites favor the formation of 2,4-diaryl-N-tosylpyrrolidines in CH2Cl2. The bipodal Fe(II) site mediates stepwise addition of nitrene to olefins to generate aziridines with good stereochemistry retention.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Pokhraj Ghosh, Molly Stauffer, Md Estak Ahmed, Jeffery A. Bertke, Richard J. Staples, Timothy H. Warren
Summary: Reduction of nitrate is a challenging chemical task in the environment and biology, but it can be facilitated by thiols, ubiquitous reductants in biology, under mild conditions. Thiols react with nitrate at a Cu-(II) center to convert it into nitric oxide, releasing a cascade of N- and S-based signaling molecules. Additionally, nitrate can be reduced to generate nitric oxide by the gasotransmitter H2S at copper-(II), revealing a crosstalk between nitrate and H2S.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Ajay Kumar Chinnam, Richard J. Staples, Jean'ne M. Shreeve
Summary: A simple synthetic strategy for bridged bis(nitramide)-based N-substituted tetrazoles is described in this study. All new compounds were isolated and fully characterized using sophisticated analytical techniques. The structures of the intermediate derivative and two final compounds were determined by single-crystal X-ray data. The thermostabilities and energetic properties of the new bridged bisnitramide-based N-substituted tetrazoles were discussed and compared with known materials.
Article
Chemistry, Multidisciplinary
Nikolaos Samartzis, Michail Athanasiou, Grigorios Raptopoulos, Patrina Paraskevopoulou, Theophilos Ioannides
Summary: Porous carbons obtained from biomass pyrolysis are an excellent choice for energy storage applications due to their abundant precursors, low cost, and the advantages of carbon aerogels such as high specific surface area, good conductivity, and light weight. Establishing cost-effective and eco-friendly protocols is significant to enhance the competitiveness of these materials. In this study, nitrogen/metal co-doped alginate-derived carbon aerogels were thoroughly characterized and showed excellent energy/power density and cycling stability in aqueous supercapacitors, surpassing previous reports.
Article
Polymer Science
Ioannis Ioannidis, Ioannis Pashalidis, Grigorios Raptopoulos, Patrina Paraskevopoulou
Summary: The removal of radionuclide/radioactivity from laboratory and environmental water samples under ambient conditions was investigated using polyurea-crosslinked calcium alginate aerogels. The removal efficiency strongly depends on the pH of the solution, with higher efficiency in acidic solutions. This study is significant for the treatment of radioactive contaminated waters using aerogel materials.
Article
Chemistry, Multidisciplinary
Fangzhou Li, Errui Li, Krishanu Samanta, Zhaoxi Zheng, Lianqian Wu, Albert D. Chen, Omar K. Farha, Richard J. Staples, Jia Niu, Klaus Schmidt-Rohr, Chenfeng Ke
Summary: In this study, a porous material with high adsorption capacity, stability, and resistance to corrosion was designed and synthesized for BF3 storage and catalysis. The material exhibited a record-high BF3 uptake capacity and was used to reduce undesired chain transfer and termination in polymerization reactions, resulting in higher molecular weights and lower polydispersity of the polymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Engineering, Environmental
Sohan Lal, Richard J. Staples, Jean'ne M. Shreeve
Summary: A variety of amine derivatives have been found to react with FOX-7, resulting in the formation of triazine derivatives that can be nitrated to produce rearranged nitramines in high yields. The structures of these compounds were determined using spectroscopic techniques, elemental analyses, and single crystal X-ray analysis. The synthesized compounds exhibited good thermal stabilities and were found to have excellent energetic properties, making them suitable candidates for solid rocket propulsion.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Organic
Sohan Lal, Richard J. Staples, Jean'ne M. Shreeve
Summary: A straightforward synthetic strategy was reported for newly designed nitrogen-rich planar explosives and solid propellants. These materials exhibit high densities (1.69-1.95 g cm(-3)), high positive enthalpies of formation (approaching 1149.21 kJ mol(-1)), promising energetic properties (P = 26.36-33.78 GPa, D = 8258-9518 m s(-1)), acceptable thermal stabilities (T (d) = 132-277°C), good sensitivities (IS = 4-40 J, FS = 60-360 N), and excellent propulsive performance (Isp = 176.80-253.06 s).
Article
Chemistry, Organic
Jatinder Singh, Richard J. J. Staples, Jeanne M. Shreeve
Summary: A strategy for synthesizing nitrogen-rich energetic materials with good properties is reported, taking advantage of the synergetic effects of inter- or intramolecular hydrogen bonds. A new thermostable and insensitive material, 1,2-dihydrazono-1,2-di(1H-tetrazol-5-5-yl)ethane, was obtained from the reaction of dioxime with hydrazinehydrate. The material has reduced acidity, low solubility in water, high nitrogen content (76%), high thermal stability (275°C), and insensitivity to external stimuli.
Article
Crystallography
Faith M. Carlson, Richard J. Staples, Shannon M. Biros
Summary: The title compound crystallizes as the bromide salt of a 50:50 mixture of (triethylazaniumyl)carboxylic acid and the zwitterionic (triethylazaniumyl)carboxylate, with the two organic entities linked by a bridging carboxylic acid hydrogen atom. The tetralkylammonium group adopts a tetrahedral shape and the carboxylic acid/carboxylate group is engaged in intramolecular hydrogen bonds.
ACTA CRYSTALLOGRAPHICA SECTION E-CRYSTALLOGRAPHIC COMMUNICATIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sudhir Lima, Maximilian H. Pohle, Michael Boehme, Helmar Goerls, Thomas Lohmiller, Alexander Schnegg, Rupam Dinda, Winfried Plass
Summary: Two new mononuclear cobalt(II) complexes (1 and 2) were synthesized using bidentate Schiff base ligands with NO donor set. X-ray structure analysis revealed a distorted pseudotetrahedral coordination sphere at the cobalt(II) ion. Magnetic susceptibility and FD-FT THz-EPR measurements, along with ab initio calculations, showed an easy-axis type of anisotropy for both complexes.
DALTON TRANSACTIONS
(2023)