Article
Chemistry, Inorganic & Nuclear
I. E. Golub, O. A. Filippov, N. V. Belkova, L. M. Epstein, E. S. Shubina
Summary: The mechanism of halogenation of decahydro-closo-decaborate dianion by HCl was explored, showing that dihydrogen-bonded complexes play a key role in the reaction process, and the increasing electrophilicity of boron atoms during substitution hinders the chlorination reaction progression.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
(2021)
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
Patrick Federmann, Tamino Bosse, Siad Wolff, Beatrice Cula, Christian Herwig, Christian Limberg
Summary: FLPs with aluminum-phosphane interactions have been synthesized using a new method, which can readily bind substrates and release strain. Additionally, this system can activate allenes for unique reactivity.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Yongliang Wei, Xiaowen Yang, Minghui Tian, Xue Wang, Tongdao Wang
Summary: The coordination of the B-H bond to a transition metal is of fundamental interest due to its relevance to the transition metal-mediated B-H bond activation mechanism and catalysis. While most reported examples involve sigma-borane/borate complexes with one or two sigma-B-H bonds, compounds with three such bonds are much less common. This study presents a facile synthesis approach for rare transition metal tris(sigma-B-H) borate complexes by salt elimination using [Cp*RuCl](4) and lithium trihydroborates Li[ArBH3] with 2,6-disubstituted aryl groups. These complexes exhibit remarkable thermal stability in solution and feature the unusual sigma-complex with three labile sigma-B-H bonds.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Yushuang Lu, Lijuan Huang, Yanan Guo, Xiaoning Yang
Summary: This study reveals that carboxyl groups play a key role in surface charge acquisition of graphene oxide (GO), and proton transfer between adjacent hydroxyl and epoxy groups can significantly affect the distribution of surface charge on GO. Computational and experimental results show good consistency, supporting the applicability of thermodynamic cycles for calculating the acidity constant of GO.
Review
Chemistry, Applied
Shintaro Kamio, Hiroto Yoshida
Summary: Recent advances in the synthesis of organoboron compounds with diminished boron Lewis acidity via B(aam)- and B(dan)-installing borylation reactions have attracted growing attention due to their unique reactivity and outstanding stability toward air and moisture. Direct Suzuki-Miyaura cross-couplings with previously believed unreactive R-B(aam)/B(dan) compounds have also been discussed.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Wei-Lian Xie, Xiao-Min Li, Jiao-Min Lin, Long-zhang Dong, Yu Chen, Ning Li, Jing-Wen Shi, Jing-Jing Liu, Jiang Liu, Shun-Li Li, Ya-Qian Lan
Summary: This study reports three sulfate groups decorated zirconium-oxo clusters as proton conductors, which exhibit high proton conductivities and stable conductivity performance, representing a promising advanced material.
Article
Chemistry, Multidisciplinary
Toren Hynes, Jason D. Masuda, Saurabh S. Chitnis
Summary: This study tested the ability to tune the acidity of planar bismuth compounds via mesomeric effects. By replacing the central nitrogen of the [N-3] pincer ligand with a less pi-donating carbon atom, the Lewis acidity at the metal can be significantly boosted. These results reveal the delicate balance between donor/acceptor and redox chemistry at planar bismuth centers.
Article
Chemistry, Inorganic & Nuclear
Sourav Bhunya, Paul M. Zimmerman, Ankan Paul
Summary: Density functional theory is used to study the mechanism of ammonia-borane (H3B-NH3, AB) regeneration from polyborazylene (BxNxHx, PBz) in the presence of hydrazine (H2N-NH2, Hz). The process of borazine (B3N3H6, Bz) digestion by hydrazine involves the formation of Lewis acid-base adducts between B atoms of Bz and Hz, followed by proton transfer. The redistribution of B-H bonds in Bz leads to the formation of hydrazine-borane (H3B-NH2NH2, HzB) and B(NHNH2)3.
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Shi-Jun Wang, Jun-Jia Zhai, Long Wang, Xiang-Ying Tang
Summary: To better understand the activity of boron catalysts, synthesizing new structural variants is an important task in boron chemistry. This study introduces a simple strategy to consecutively regulate the catalytic activity of B(C6F5)3& H2O by adding an appropriate amount of tetrahydrofuran. The superiority of this strategy is demonstrated through a challenging nucleophilic substitution reaction of benzyl fluoride with alcohol.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Inorganic & Nuclear
Jiang He, Florian Rauch, Ivo Krummenacher, Holger Braunschweig, Maik Finze, Todd B. Marder
Summary: Two derivatives of phenylpyridyl-fused boroles were prepared by functionalizing the pyridyl groups to introduce an electron-rich dihydropyridine moiety (compound 1) and an electron-deficient N-methylpyridinium cation (compound 2). Compound 1 showed a cathodically shifted reduction potential due to strong conjugation, while compound 2 exhibited extreme electron deficiency with significantly anodically shifted reduction potential and reversible coordination of THF. Photophysical properties of both compounds in different solvents were studied, with theoretical analysis supporting strong conjugation in compound 1 and the electron-deficient nature of compound 2.
DALTON TRANSACTIONS
(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.
Article
Chemistry, Physical
Zheng-Wang Qu, Hui Zhu, Rainer Streubel, Stefan Grimme
Summary: Extensive DFT calculations demonstrate that BH3NH3 can transfer hydrogen to CO2 as separated hydride and proton rather than HCO3- in water, with a barrier energy of 25.9 kcal mol(-1). Subsequently, borate anions facilitate faster hydrogen transfer to electrophilic CO2, protic H2O, or HCO2H, resulting in competitive formate production and H-2 release.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Tomohiro Fukushima, Hidetaka Hasebe, Kei Murakoshi
Summary: This study highlights the tunability of proton permeation by the presence of covalently bonded molecules in modified single-layer graphene structures, offering a new approach for designing tunable interfaces for proton permeation. Energy calculations were used to evaluate the barrier height and permeation rate, providing insights into the theoretical study of proton permeation ability.
Article
Chemistry, Organic
Jin Wang, Ming-Yue Ju, Xinghua Wang, Yan-Na Ma, Donghui Wei, Xuenian Chen
Summary: The hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3](2), NaADBH) to form primary alcohols were systematically investigated, demonstrating that NaADBH is a promising reducing agent due to its stability and efficiency. The reduction mechanism was elucidated experimentally and computationally, with intermediates and byproducts identified through B-11 and H-1 NMR. The reactions exhibit excellent yields and good selectivity, providing alternative synthetic approaches for the conversion of carboxylic acids to primary alcohols with a wide range of functional group tolerance.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
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, 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)
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)
