Article
Chemistry, Organic
Zhen Li, Jin-Dong Yang, Jin-Pei Cheng
Summary: Base-promoted hydride transfer (BPHyT) strategy was studied in a three-component system, showing that the base plays a crucial role in regulating the reaction kinetics compared to traditional Bronsted acid or base catalysis. Structure-reactivity relationships revealed that both the hydride acceptor and the base contribute equally to control the kinetics of BPHyT. Kinetic isotope effects suggested the involvement of hydride transfer in the rate-determining step, confirming the feasibility of applying BPHyT in organic synthesis.
ORGANIC CHEMISTRY FRONTIERS
(2021)
Review
Crystallography
Nuraini Ruslan, Muhammad Syarifuddin Yahya, Md Nurul Islam Siddique, Ashish Prabhakar Yengantiwar, Mohammad Ismail, Md Rabiul Awal, Mohd Zaki Mohd Yusoff, Muhammad Firdaus Asyraf Abdul Halim Yap, Nurul Shafikah Mustafa
Summary: Metal hydrides such as MgH2 and NaBH4 have high potential for solid-state hydrogen storage. However, a dehydrogenation process is required prior to hydrogen utilization. The hydrolysis method is a possible way to extract or generate hydrogen, but issues like passivation layer, high cost and sluggish self-hydrolysis can be overcome with the help of catalysts. Studies have shown that adding catalysts like chloride, oxide, fluoride, platinum, ruthenium, cobalt, and nickel can significantly enhance the amount of hydrogen released during the hydrolysis of MgH2 and NaBH4.
Article
Chemistry, Physical
Xin Zhang, Lingchao Zhang, Wenxuan Zhang, Zhuanghe Ren, Zhenguo Huang, Jianjiang Hu, Mingxia Gao, Hongge Pan, Yongfeng Liu
Summary: This work presents an effective synthetic strategy for low-temperature and highly reversible hydrogen cycling with LiBH4 nanocomposite, showing superior hydrogen sorption capabilities and stable cyclability. The key factor influencing hydrogen cycling is the reactivity of boron, which has been successfully addressed in this study. The synergistic effects of nanostructuring and nanocatalysis contribute to efficient formation of BH4- hydrogenation and elemental boron during dehydrogenation process, shedding light on new strategies for practical hydrogen storage applications in borohydride family.
Article
Chemistry, Physical
Santhosh Gatreddi, Dexin Sui, Robert P. Hausinger, Jian Hu
Summary: The nickel-pincer nucleotide (NPN) cofactor in LarALp plays an essential role in the activities of racemases/epimerases in the LarA superfamily. By using sodium borohydride (NaBH4), it was found that LarALp can be irreversibly inactivated with a color change. High-resolution structures of LarALp revealed a weakened C- Ni bond in the sulfite-NPN adduct, providing insights into the mechanism of LarALp inactivation by NaBH4.
Article
Engineering, Environmental
Yongyang Zhu, Shaoyang Shen, Liuzhang Ouyang, Jiangwen Liu, Hui Wang, Zhenguo Huang, Min Zhu
Summary: This study reports an economical method to synthesize Mg(BH4)(2) by converting B-O bonds in widely available borates or boric acid to B-H. This method avoids expensive boron sources and high pressure and temperature conditions, significantly reducing costs, and could be an alternative to the current synthesis processes of Mg(BH4)(2).
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Engineering, Environmental
Geo Jong Kim, Hyun Tae Hwang
Summary: Hydrogen from sodium borohydride can be generated by thermolysis or hydrolysis, but both methods have drawbacks such as high temperatures required or safety concerns. A new process, thermal hydrolysis of SBH, is proposed to address these issues and achieve efficient hydrogen production.
CHEMICAL ENGINEERING JOURNAL
(2021)
Article
Energy & Fuels
N. S. C. Mazlan, F. A. Halim Yap, M. S. Yahya, S. B. Mohamed, N. A. Sazelee, N. A. Ali, I. Jusoh, M. Ismail
Summary: This study focuses on the catalytic effect of TiF3 on the hydrogen storage properties of the MgH2-Na3AlH6-LiBH4 system produced by ball milling. The addition of TiF3 catalyst results in a faster hydrogen uptake and release rate compared to the catalyst-free system. The apparent activation energy for the dissociation of Li3AlH6, MgH2, and NaBH4 in the TiF3-doped composite is significantly reduced. TiF3's catalytic performance is attributed to the in-situ production of Al-Ti and Al-F phases during the dehydrogenation process.
JOURNAL OF ENERGY STORAGE
(2023)
Article
Biochemistry & Molecular Biology
Igor E. Golub, Oleg A. Filippov, Natalia V. Belkova, Lina M. Epstein, Elena S. Shubina
Summary: The study established the mechanism of consecutive halogenation of borohydrides and hexahydro-closo-hexaborate dianion by hydrogen halides, revealing changes in the chemical properties of borohydrides during halogenation.
Article
Chemistry, Organic
Ekaterina S. Kudriashova, Margarita A. Yarushina, Andrei E. Gavryushin, Ivan D. Grishin, Yulia B. Malysheva, Vasilii F. Otvagin, Alexey Yu. Fedorov
Summary: We report an unusual one-pot preparation of α-benzyl-substituted conjugated enals via ZnCl2/LiCl/H2O-mediated transformation of styrenes. Through experimental and computational studies, we propose an underlying mechanism involving electrophilic addition and hydride transfer with iminium cations. The effect of the LiCl/ZnCl2/H2O combination on the reaction yield and the activation of iminium electrophile have been demonstrated.
Article
Chemistry, Physical
Hui Luo, Yunshu Yang, Liwen Lu, Guangxu Li, Xinhua Wang, Xiantun Huang, Xiaoma Tao, Cunke Huang, Zhiqiang Lan, Wenzheng Zhou, Jin Guo, Haizhen Liu
Summary: In this study, a two-dimensional Ti3CN MXene was synthesized and added to the Li-Mg-B-H composite, resulting in a reduction in the dehydrogenation temperature and induction period of the composite. The reversible capacity and capacity retention ratio of the composite were maintained at high levels. Micro-structure studies revealed the transformation of Ti3CN into highly-dispersed nano-TiB2, which acted as an active catalyst to improve the kinetics and reversibility of the composite. This research provides insights into the role of MXene in tailoring the hydrogen storage properties of metal borohydride-based composites.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
R. Joseph Lastowski, Jonathan T. Yarranton, Lingyang Zhu, Konstantinos D. Vogiatzis, Gregory S. Girolami
Summary: We have described new compounds M(CH2NMe2BH3)(3) (M = Ti, Cr, and Co), each containing three chelating BDAM ligands. The BDAM anion is bound to the metal center through a metal-carbon sigma bond and a three-center M-H-B interaction. The titanium(III) compound is trigonal prismatic, while the chromium(III) and cobalt(III) compounds are both fac-octahedral. The chromium and cobalt compounds exhibit rapid dynamic processes in solution: interchange of enantiomers and interchange of hydrogen atoms on boron. The UV-vis absorption spectra show large ligand field splittings caused by the M-H-B interactions, and DFT calculations suggest that these properties are due in part to the delocalization of electron density away from the metal center.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Terry D. Humphries, Mark Paskevicius, Ali Alamri, Craig E. Buckley
Summary: Thermal batteries are efficient for storing renewable energies, utilizing reversible thermochemical reactions to drive a heat engine. Studies on the SrH2-2Al system have shown promising properties for high efficiency operation, which could enhance technological applications.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Chemistry, Physical
Meryem Sena Akkus
Summary: In the current global energy crisis, the value of hydrogen has gained more recognition. Metal borohydrides, rich in hydrogen, have attracted significant attention from researchers. In this study, glass microscope slides were coated with nickel nanorods and used as a catalyst for catalytic hydrolysis reactions of dimethylamine borane and lithium borohydride to produce hydrogen. Various parameters were varied and their effects on the catalyst's performance were examined. The study also determined the reaction kinetics and activation energy values of dimethylamine borane and lithium borohydride.
Article
Chemistry, Multidisciplinary
Joseph E. Schneider, McKenna K. Goetz, John S. Anderson
Summary: Transition metal oxo species play a crucial role in activating strong C-H bonds. While various parameters have been proposed to determine their reactivity, only thermodynamic parameters are statistically significant in influencing their ability to mediate C-H activation. Notably, the oxidation potential and basicity of the oxo complexes also make independent and significant contributions, suggesting a more complex thermodynamic landscape than previously thought.
Article
Chemistry, Physical
Sruthy Balakrishnan, Terry D. Humphries, Mark Paskevicius, Craig E. Buckley
Summary: Calcium hydride has shown potential as a hydrogen storage and thermochemical energy storage material, but its high operating temperature has limited its application and research on its hydrogen sorption thermodynamics. This study provides experimental data on the thermodynamic properties and activation energy of CaH2 in both solid and molten states, filling the gap in the thermodynamics of the Ca-H system for the first time in over 60 years.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
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
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
Alexey N. Bilyachenko, Evgenii I. Gutsul, Victor N. Khrustalev, Pavel V. Dorovatovskii, Elena S. Shubina, Yannick Guari, Gautier Felix, Joulia Larionova, Abdallah G. Mahmoud, Armando J. L. Pombeiro
Summary: The study presents a new feature in the self-assembly of manganese-based phenylsilsesquioxanes and investigates the influence of acetone solvates on cage structure formation. A series of new manganese-based silsesquioxane complexes with different ligands were synthesized and characterized. Several compounds exhibit unique cagelike metallasilsesquioxane molecular architectures. The catalytic performance of a representative precatalyst was examined for the microwave-assisted oxidation reaction.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Inorganic & Nuclear
Alexey N. Bilyachenko, Evgenii I. Gutsul, Victor N. Khrustalev, Olga Chusova, Pavel V. Dorovatovskii, Vusala A. Aliyeva, Ana B. Paninho, Ana V. M. Nunes, Kamran T. Mahmudov, Elena S. Shubina, Armando J. L. Pombeiro
Summary: This study reports a novel family of cage manganesesilsesquioxanes prepared via complexation with bathophenanthroline. The compounds exhibit several unprecedented cage metallasilsesquioxane structural features and show fungicidal activity and catalytic effects.
INORGANIC CHEMISTRY
(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)
Article
Chemistry, Inorganic & Nuclear
Guojun Hu, Ziyue Deng, Yanwei Wang, Dan Yuan, Yong Zhang, Yingming Yao
Summary: A series of rare-earth metal complexes were synthesized and used as efficient initiators for the polymerization of trimethylene carbonate (TMC) and (L)-lactide ((L)-LA).
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Van Ha Nguyen, John H. K. Yip
Summary: In this study, eight PtII-azulene complexes were synthesized to investigate the effect of metalation on the electronic structures, spectroscopy, and luminescence of organic chromophores. The results showed that the attachment of Pt substituents to azulene affected the HOMOs, LUMOs, and luminescence properties. The study provides insights into the role of metalation in modifying the properties of organic chromophores.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Moon Kedia, Virender Singh, Bhaskaran Shankar, Malaichamy Sathiyendiran
Summary: This study synthesized two types of neutral binuclear metallocycles using a one-pot solvothermal method and characterized their structures. The analysis revealed that these complexes adopt a binuclear heteroleptic cyclic architecture and belong to phosphine oxide donor (P=O)-based supramolecular coordination cyclic complexes.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Radhey S. Srivastava
Summary: This study demonstrates the effectiveness of zero-valent elements as reductants for the deoxydehydration reaction of polyols catalyzed by ONO-pincer ligated molybdenum dioxo. The insolubility and easy separability of the reductants and their oxidized products during the reaction are emphasized. Additionally, the choice of ligand has an impact on the catalytic performance of the reaction.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Hao Zhou, Yajun Sun, Li Deng, Weiran Yang, Yuehui Li
Summary: Efficient Ru-catalyzed hydrogenation of aldehydes was achieved using carbazole-derived phosphine ligands, with the crucial role of N-H moiety in promoting the catalytic reaction. The method was successfully applied in the Co/Ru-catalyzed hydroformylation process, resulting in the production of long-chain alcohols with excellent yields.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Theodor Danescu, Alexandru Lupan, Radu Silaghi-Dumitrescu, R. Bruce King
Summary: The structures and energies of complexes containing (Me2C2N2P)2Ru2(CO)n and (Me2C2N2P)2Fe2(CO)n have been studied. Low-energy structures are characterized by the presence of bridging diazaphospholyl rings, while higher-energy structures involve different ligand structures.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Savannah C. Kapper, Aamani Ponnekanti, Jonas Schaab, Tian-yi Li, Christine L. Chung, Gael Ung, Peter I. Djurovich, Mark E. Thompson
Summary: Organometallic iridium complexes with two cyclometalated ligands and one bis-oxazoline derived ancillary ligand were studied. These complexes have emission spanning across the visible and near-ultraviolet region, with moderate to high photoluminescence quantum yields. The (ppy)2Ir(BOX-CN) complexes were resolved into Delta- and Lambda-diastereomers based on solubility differences.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Zahra Karimi Sangari, Hossein Naeimi
Summary: In this research, a nanostructured CoCuFe2O4 catalyst was prepared using a brief and useful synthetic strategy. This catalyst was used for synthesizing 1,2,4,5-tetrasubstituted imidazole derivatives under ultrasonic irradiation. The approach offers advantages such as high efficiency, short reaction times, simplicity of the reaction medium, accelerated reaction rates, and easier separation and purification of products.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Rukhsana Gul, Wajid Munir, Ebraheem Abdu Musad Saleh, Shaukat Shujah, Muhammad Sirajuddin, Saira Tabassum, Khalil Ur Rehman, Dilfaraz Khan, Sameerah I. Al-Saeedi, Ehab A. Abdelrahman
Summary: Two new Schiff base ligands were synthesized and used to form copper, nickel, and cobalt complexes. The synthesized compounds were characterized and screened for various biological activities. The metal complexes showed better activities in antibacterial, antifungal, antidiabetic, and antioxidant assays.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Review
Chemistry, Inorganic & Nuclear
Ahsan Nazir, Pengwei Huo, Ameena Tur Rasool
Summary: This review explores the potential of g-C3N4-based S-scheme heterojunctions in addressing environmental issues. It summarizes the mechanism and preparation techniques of S-scheme heterojunctions based on g-C3N4, and presents recent studies on their applications in pollutant removal, CO2 reduction, hydrogen production, and bacterial disinfection. The review concludes with an outlook on future challenges for g-C3N4-based S-scheme heterojunctions.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Francois Mazars, Koffi Senam Etse, Guillermo Zaragoza, Lionel Delaude
Summary: The activity of three Pd-PEPPSI catalyst precursors with N-heterocyclic carbene (NHC) ligands derived from caffeine and theophylline in Mizoroki-Heck reactions was tested. The results showed that the catalysts achieved high conversions and yields, especially in the presence of electron-withdrawing substituents.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
Article
Chemistry, Inorganic & Nuclear
Bo-Han Wu, Xue Zhou, Lin Liu, Zheng-Bo Han
Summary: Researching carbon dioxide removal from flue gas and natural gas is crucial. Metal-organic frameworks (MOFs) are commonly used in adsorption due to their high surface area, porosity, and chemical properties. An ultra-microporous MOF CPM-20(Co) with mixed ligand was synthesized using inexpensive ligands. The material exhibited high selectivities and low regenerative energy, making it a promising option for CO2 separation in industries.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2024)
