Review
Chemistry, Inorganic & Nuclear
Natalia Belkova, Oleg A. Filippov, Elena S. Osipova, Sergey Safronov, Lina M. Epstein, Elena S. Shubina
Summary: Transition-metal hydride complexes are abundant in organometallic chemistry, with their reactivity determined by homolytic and heterolytic cleavage of M-H bonds. Late transition metal hydrides are often supported by phosphine ligands, allowing for systematic tuning of electronic and steric properties at the metal center. The influence of phosphine properties on the reactivity of transition metal hydrides in stoichiometric and catalytic processes is traced in this review, highlighting the role of hydrogen bonding interactions in hydrogen transfer reactions.
COORDINATION CHEMISTRY REVIEWS
(2021)
Article
Engineering, Environmental
Huawei Huang, Liangliang Xu, Dong Yoon Woo, Seongbeen Kim, Sung Min Kim, Yong Kyeong Kim, Jaeho Byeon, Jinwoo Lee
Summary: Anion-exchange membrane water electrolyzer is a promising and green technology for hydrogen production. This study presents a strategy to optimize the morphology and surface properties of WO2.7 to improve the efficiency of the water dissociation step. Experimental analysis demonstrates that Co-WO2.7-x and Ni-WO2.7-x have a larger electrochemical surface area, and Co-WO2.7-x has the lowest energy barrier, resulting in lower overpotential and higher current.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Mahvash Afzal, Nandlal Gupta, Aashish Mallik, K. S. Vishnulal, Pratibha Sharma
Summary: This study continues the computational analysis of a reactor with hexagonal honeycomb-based heat transfer enhancements, investigating the performance of a metal alloy and the reactor experimentally. It determines the gravimetric capacity and reaction kinetics of the alloy La0.9Ce0.1Ni5, while also exploring the impact of operating conditions on reactor performance. Additionally, evaporative cooling is tested for the first time as a heat removal technique for metal hydride based hydrogen storage reactors and found to significantly improve heat transfer.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Multidisciplinary Sciences
Nathan Dasenbrock-Gammon, Elliot Snider, Raymond McBride, Hiranya Pasan, Dylan Durkee, Nugzari Khalvashi-Sutter, Sasanka Munasinghe, Sachith E. E. Dissanayake, Keith V. V. Lawler, Ashkan Salamat, Ranga P. P. Dias
Summary: By studying a nitrogen-doped lutetium hydride, we have discovered a superconductor with a maximum critical superconducting transition temperature (T-c) of 294 K, which means superconductivity at room temperature and near-ambient pressures.
Article
Chemistry, Physical
Qinfu Zhao, Lei Chen, Bingbing Suo, Zhiyong Zhang, Dan Deng, Bo Zhou, Haiyan Zhu, Qi Song
Summary: Inspired by alkaline metal borohydrides and organic-inorganic hybrid perovskite, a complex structure of (CH3NH3)BH4 with high hydrogen capacity is predicted. Through analysis of electronic structures, it is concluded that (CH3NH3)BH4 can be synthesized by a substitution reaction. The structural symmetries, elastic constants, and electronic properties of (CH3NH3)BH4 are investigated, showing strong elastic anisotropy and the influence of a planar dihydrogen bonding network on the dehydrogenation reaction. The proposed dehydrogenation process of (CH3NH3)BH4 via intermediate compounds suggests that it can decompose spontaneously, similar to ammonium borohydride.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Chemistry, Multidisciplinary
Andryj M. Borys, Lorraine A. Malaspina, Simon Grabowsky, Eva Hevia
Summary: Through the study of the family of organonickelate complexes, we have discovered a rare class of low-valent transition metal complexes with repulsive Ni-Li interactions, forming tri-coordinated structures. Additionally, London dispersion forces play a crucial role in the stabilization and isolation of these complexes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Materials Science, Multidisciplinary
Xin F. Tan, Manjin Kim, Kazuhiro Yasuda, Kazuhiro Nogita
Summary: Bulk Mg-based hydrogen storage materials have the potential to provide a low-cost solution for energy storage and transportation. They are safer and more oxidation resistant compared to nano powders. Various alloying elements and innovative processing methods can be used to improve the performance of bulk Mg alloys in terms of hydrogen sorption kinetics and stability.
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
(2023)
Article
Materials Science, Multidisciplinary
Luca Chiari, Kenji Kojima, Yusuke Endo, Hiroki Teshigahara, Maik Butterling, Maciej Oskar Liedke, Eric Hirschmann, Ahmed G. Attallah, Andeas Wagner, Masanori Fujinami
Summary: The formation and evolution of hydrogen-induced defects in nickel were investigated using positron annihilation lifetime spectroscopy, revealing that hydrogen addition at room temperature can lead to the formation of a large number of atomic vacancies. These defects in nickel agglomerate into large vacancy clusters during room temperature aging, demonstrating the primary role of hydrogen in the formation and stabilization of vacancies.
Article
Chemistry, Physical
Aditya Sundar, Yuqing Huang, Jianguo Yu, M. Nedim Cinbiz
Summary: Solid state hydrides, such as early transition metal hydrides, play a crucial role in the future of hydrogen energy. This study reveals the intricate bonding features and electron structure differences between early transition metal hydrides and alkali/alkaline earth metal hydrides, shedding light on their hydrogen retention and transport behavior.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2022)
Article
Chemistry, Multidisciplinary
Zhengang Ke, Yuepeng Wang, Yanfei Zhao, Minhao Tang, Wei Zeng, Ying Wang, Xiaoqian Chang, Buxing Han, Zhimin Liu
Summary: In this study, an ionic-liquid (IL) hydrogen-bonding promoted dihydrogen auto-transfer strategy was used for the amination of alcohols to higher amines over a cobalt catalyst under base-free conditions. The strategy demonstrated high performance and tolerance to a wide range of amines and alcohols, resulting in good to excellent yields of higher amines. The mechanism investigation suggested that the [BF4] anion played a key role in activating the alcohol and facilitating the transfer of hydrogen atoms to the cobalt catalyst, leading to the formation of aldehyde intermediates and cobalt dihydride complexes, which were involved in the subsequent reductive amination. This green and effective route for alcohol amination has potential applications in alcohol-involved alkylation reactions.
Article
Chemistry, Physical
Yang Meng, Shunlong Ju, Wei Chen, Xiaowei Chen, Guanglin Xia, Dalin Sun, Xuebin Yu
Summary: By fabricating V4Nb18O55 microspheres, the H-2 desorption and absorption properties of MgH2 can be improved and the uniform formation of Nb/V interfaces can be achieved, resulting in the reduction of dehydrogenation temperature of MgH2 and the enhancement of hydrogenation reaction rate.
Review
Energy & Fuels
Nejc Klopcic, Ilena Grimmer, Franz Winkler, Markus Sartory, Alexander Trattner
Summary: Efficient energy storage is crucial for the shift to renewable energies, and hydrogen storage in metal hydrides offers high energy densities and safety advantages. This work investigates the technical, economic, and environmental aspects of different metal hydride materials, including their properties, production methods, and potential enhancements. The impacts on material costs, raw material abundance, and import dependency are discussed, and the advantages and disadvantages of selected materials are derived for material selection. Further research on material properties and system-level improvements is needed for widespread application of metal hydrides.
JOURNAL OF ENERGY STORAGE
(2023)
Review
Chemistry, Physical
N. A. Ali, N. A. Sazelee, M. Ismail
Summary: Metal hydrides and complex hydrides are the most convenient method for hydrogen storage, offering high hydrogen capacity, but facing challenges of high operating temperature and low reversibility.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2021)
Article
Chemistry, Multidisciplinary
Elena S. Osipova, Ekaterina S. Gulyaeva, Evgenii I. Gutsul, Vladislava A. Kirkina, Alexander A. Pavlov, Yulia V. Nelyubina, Andrea Rossin, Maurizio Peruzzini, Lina M. Epstein, Natalia V. Belkova, Oleg A. Filippov, Elena S. Shubina
Summary: The reaction between basic [(PCP)Pd(H)] and acidic [LWH(CO)(3)] leads to the formation of bimolecular complexes that catalyze dehydrogenation. Experimental and computational studies reveal the formation of a complex in the first step, where proton transfer is the rate-determining step.
Review
Chemistry, Multidisciplinary
Vladimir Zelenak, Ivan Saldan
Summary: Metal-organic frameworks (MOFs) show promise for hydrogen storage, with reversible and high-rate hydrogen adsorption as main benefits, but operation at very low temperatures as a drawback. Factors affecting hydrogen adsorption in MOFs are studied, and nanoconfinement of metal hydrides inside MOFs is proposed as a new approach for hydrogen storage. Incorporating metal nanoparticles in MOFs for future prospects as nanoscaffolds and/or H-2 sorbents is summarized.
Article
Biochemistry & Molecular Biology
Alexey N. Bilyachenko, Ivan S. Arteev, Victor N. Khrustalev, Anna Y. Zueva, Lidia S. Shul'pina, Elena S. Shubina, Nikolay S. Ikonnikov, Georgiy B. Shul'pin
Summary: A family of octacopper cage methylsilsesquioxanes with prismatic structures has been synthesized and characterized. The distortion of the prismatic cages was found to be influenced by additional alkaline metal ions, solvating ligands, and encapsulating species. Opportunities for designing supramolecular 1D structures were identified, such as formate linkers between copper centers and crown ether-like contacts between cesium ions and siloxane cycles. The Cu8Cs2-based complex 4 exhibited high catalytic activity in alkane and alcohol oxidation reactions.
Article
Biochemistry & Molecular Biology
Gleb B. Yakovlev, Aleksei A. Titov, Alexander F. Smol'yakov, Andrey Yu. Chernyadyev, Oleg A. Filippov, Elena S. Shubina
Summary: The reaction between a cyclic trinuclear copper(I) or silver(I) pyrazolate complex and 1,1'-dimethyl-2,2'-bibenzimidazole can result in the formation of tetranuclear adducts decorated by one or two molecules of a diimine ligand. The coordination of the ligand can stabilize the formation of a tetrahedral core in the copper-containing complex and a distorted tetrahedron in the silver analog. Complexes with one diimine molecule possess two types of metals and exhibit significantly distorted central cores. Temperature decrease and solid-state structure activate triplet states, leading to phosphorescence. The silver-containing complex exhibits dual emission even at room temperature.
Article
Chemistry, Inorganic & Nuclear
Matthieu Cavailles, Oleg A. Filippov, Vincent Cesar, Noel Lugan, Dmitry A. Valyaev
Summary: The first manganese complex with a chiral N-heterocyclic carbene (NHC) ligand was synthesized and characterized. The existence of two isomers with distinct nu(CO) band patterns in solution was revealed by IR spectroscopy. DFT calculations explained their different spectroscopic properties as a result of attractive intramolecular interligand interactions.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Elena S. Osipova, Sergey A. Kovalenko, Ekaterina S. Gulyaeva, Nikolay V. Kireev, Alexander A. Pavlov, Oleg A. Filippov, Anastasia A. Danshina, Dmitry A. Valyaev, Yves Canac, Elena S. Shubina, Natalia V. Belkova
Summary: The acid-base characteristics of metal hydride complexes can be used to predict their activity in catalytic reactions. The polarity of the M-H bond changes during the formation of a non-covalent adduct with an acidic or basic partner, which is responsible for the subsequent hydrogen ion transfer.
Article
Chemistry, Inorganic & Nuclear
Elena S. Osipova, Daria V. Sedlova, Evgenii I. Gutsul, Yulia V. Nelyubina, Pavel V. Dorovatovskii, Lina M. Epstein, Oleg A. Filippov, Natalia V. Belkova, Elena S. Shubina
Summary: This study found that a series of bimetallic complexes catalyze formic acid decomposition into H2/CO2 under mild conditions without any organic base additives. The catalytic activity of the complexes increases with CH2-substitution of the O-bridges and the proton-donating ability of the Mo/W hydride. The best result was obtained with (tBuPCP)Pd(mu-OC)Mo(CO)2Cp (3), which showed complete conversion at 2 mol % loading in 30 min at 50 degrees C (TOF = 100 h-1). The experimental data also showed the involvement of palladium hydride species and the interaction of formates with Bro''nsted or Lewis acids in the catalytic cycle.
Article
Chemistry, Inorganic & Nuclear
Gautier Felix, Alena Kulakova, Saad Sene, Clement Charlot, Alexey N. Bilyachenko, Alexander A. Korlyukov, Alexander D. Volodin, Elena S. Shubina, Ilia G. Elizbarian, Yannick Guari, Joulia Larionova
Summary: We report the synthesis, structures, magnetic, and luminescence properties of a new series of tetranuclear lanthanide-based germsesquioxanes. These compounds exhibit characteristic Ln3+-based emission in solid state at room and liquid nitrogen temperature. The mixed Tb3+/Eu3+ compound works as a self-referenced ratiometric optical thermometer with a maximum relative sensitivity of 0.87% °C-1 achieved at 57.6 degrees C.
Article
Chemistry, Physical
Sylwia Kostera, Stefan Weber, Ines Blaha, Maurizio Peruzzini, Karl Kirchner, Luca Gonsalvi
Summary: Well-defined, bench-stable Mn(I) non-pincer-type complexes were used as catalysts for the selective reduction of CO2 to boryl-protected MeOH in the presence of pinacolborane (HBpin). High yields were achieved under mild reaction conditions without the need for base or additives, using the alkylcarbonyl Mn(I) bis(phosphine) complexes fac-[Mn(CH2CH2CH3)(dippe)(CO)3] [Mn1, dippe = 1,2-bis(diisopropylphosphino)ethane] and [Mn(dippe)(CO)2{(mu-H)2(Bpin)}] (Mn4) as precatalysts. Mechanistic insights were obtained through NMR experiments and monitoring of the catalytic reactions.
Article
Chemistry, Inorganic & Nuclear
Arina Olbrykh, Aleksei Titov, Alexander Smol'yakov, Oleg Filippov, Elena S. Shubina
Summary: The investigation studied the interaction of cyclic trinuclear silver(I) pyrazolate [AgPz](3) with pyridine-based chalcones through various spectroscopic techniques. The carbonyl group participated in coordination with metal ions, while non-covalent pi-pi/M-pi interactions played a major role in complex formation. The structures of the complexes were retained in both solution and solid state. Isomerization affected the complexation of anthracene-containing chalcones, with E-isomer seeking a planar structure and Z-isomer showing chelating coordination. The complexation of anthracene-containing chalcones allowed a change in emission nature, while phenyl-substituted chalcone demonstrated a significant shift in emission energy compared to the free base when complexed with a macrocycle.
Article
Chemistry, Multidisciplinary
Sylwia Kostera, Gabriele Manca, Luca Gonsalvi
Summary: Catalytic hydrogenation of CO2 to formate was achieved using the neutral, halide-free, coordinatively saturated tris(carbonyl) manganese pincer-type complex [Mn(PNP)(CO)(3)] as catalyst, DBU as base, and LiOTf as Lewis acid additive. The reaction conditions were mild (60 bar, 80°C). DFT calculations revealed that the activation of the precatalyst occurred through intermolecular, base-assisted dihydrogen heterolytic splitting.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexey N. Bilyachenko, Ivan S. Arteev, Victor N. Khrustalev, Lidia S. Shul'pina, Alexander A. Korlyukov, Nikolay S. Ikonnikov, Elena S. Shubina, Yuriy N. Kozlov, Nuno Reis Conceicao, M. Fatima C. Guedes da Silva, Kamran T. Mahmudov, Armando J. L. Pombeiro
Summary: Nonanuclear Cu5Cs4-based phenylsilsesquioxanes exhibit unprecedented Si-14-based cyclic silsesquioxane ligand, nontrivial nuclearity, supramolecular organization, and catalytic activity in the mild oxidative functionalization of alkanes and alcohols, and in the Baeyer-Villiger oxidation of cyclohexanone, and in the tandem cyclohexane oxidation/B-V oxidation of cyclohexanone.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Gautier Felix, Saad Sene, Alena Kulakova, Alexey N. Bilyachenko, Victor N. Khrustalev, Elena S. Shubina, Yannick Guari, Joulia Larionova
Summary: In this article, the synthesis, structures, and luminescent properties of a series of tetranuclear lanthanide-silsesquioxane compounds were reported. The impact of different combinations of lanthanide ions on magnetic and photo-luminescent properties was investigated.
Review
Chemistry, Multidisciplinary
N. V. Kireev, O. A. Filippov, L. M. Epstein, E. S. Shubina, N. V. Belkova
Summary: This review focuses on the reactivity of dinitrogen complexes of group 6 metals with phosphine ligands. It identifies the main stages of N-2 reduction and factors affecting the reaction efficiency. The protonation of the coordinated N-2 molecule, which occurs through alternating proton and electron transfer steps, is highlighted as a key step in the catalytic cycle of nitrogen reduction.
RUSSIAN CHEMICAL BULLETIN
(2023)
