Article
Chemistry, Inorganic & Nuclear
Krzysztof Fink, Jakub Cebula, Zdenek Tosner, Mateusz Psurski, Mariusz Uchman, Tomasz M. Goszczynski
Summary: Cobalt bis(dicarbollide) (COSAN) is a versatile metallacarborane used in drug development. This study comprehensively characterized the interactions between COSAN and DNA, finding that COSAN has no significant effect on DNA structure and can induce cytotoxicity even without DNA presence. These findings confirm the safety and biocompatibility of metallacarboranes and provide new opportunities for drug development.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Wei Yang, Rong Jiang, Chao Liu, Baoqiu Yu, Xue Cai, Hailong Wang
Summary: Two chalcogen-bonded organic frameworks, CBOF-1 and CBOF-2, were constructed with structural porosity facilitated by a combination of chalcogen bonding and Se center dot center dot center dot pi interactions. CBOF-1 exhibited higher porosity with open pore channels, while CBOF-2 had lower accessible pore volume percentage filled by tetrahydrofuran molecules.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Biochemistry & Molecular Biology
Krzysztof Smialkowski, Carla Sardo, Zbigniew J. J. Lesnikowski
Summary: The exploitation of metallacarboranes' potential in various fields requires convenient and versatile methods for their functionalization. This study reports the functionalization of cobalt bis(1,2-dicarbollide) at 8,8 '-boron atoms with different heterobifunctional moieties. It also describes an approach to the synthesis of three and four functionalized metallacarboranes simultaneously at boron and carbon atoms.
Review
Biochemistry & Molecular Biology
Lucia Pazderova, Ece Zeynep Tuzun, Dmytro Bavol, Miroslava Litecka, Lukas Fojt, Bohumir Gruner
Summary: The cobalt bis(dicarbollide)(1(-)) anion plays a significant role in material science and medicine due to its unique properties and the availability of synthetic routes for easy modifications. The modification of the dicarbollide cage has been well-established for boron atom substitutions, but there has been limited progress on carbon vertex modifications. Recent developments in metalation reactions on C-H vertices have enabled direct and straightforward cage modifications, leading to new trends in the field. This review provides an overview of these methods and their applications in designing unconventional drugs.
Article
Chemistry, Multidisciplinary
Isabel Guerrero, Clara Vinas, Isabel Romero, Francesc Teixidor
Summary: The cobalt bis(dicarbollide) complex Na[3,3'-Co(eta(5)-1,2-C2B9H11) (Na[1]) is an effective photoredox catalyst for the oxidation of alkenes to epoxides in water, exhibiting high efficiency and selectivity compared to other photosensitizers. By adjusting the catalyst loading, different product selectivity and conversion rates can be achieved in the reaction.
Article
Biochemistry & Molecular Biology
Fengying Lei, Qingyu Liu, Yeshuang Zhong, Xinai Cui, Jie Yu, Zuquan Hu, Gang Feng, Zhu Zeng, Tao Lu
Summary: In recent years, there has been substantial research interest in the non-covalent interactions between chalcogen centers. This study systematically investigates the pi-hole-type interactions between chalcogen centers in model complexes, and reveals their significant impact on the stability of the complexes.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Multidisciplinary
Runxia Nan, Yiwen Li, Zhouli Zhu, Fan Qi, Xu-Qiong Xiao
Summary: This study focused on the synthesis and transformation of functional groups in metallacarboranes, and investigated their impact on the structure and properties of the metallacarborane framework.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rebekah J. Jeans, Georgina M. Rosair, Alan J. Welch
Summary: This study presents the first example of controlled isomerization of a C,C'-bound bis(ortho-carborane) ligand to a C,B'-bound form without altering the rest of the molecule's structure. The different electron-donating properties of the C and B vertices in carboranes allow for fine-tuning the reactivity of the metal center.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Robin Weiss, Emmanuel Aubert, Loic Groslambert, Patrick Pale, Victor Mamane
Summary: In the field of noncovalent interactions, chalcogen bonding (ChB) involving the tellurium atom is currently of great interest in supramolecular chemistry and catalysis. The formation and strength of ChB should be studied in solution before its application. New tellurium derivatives with CH2F and CF3 groups were synthesized to demonstrate Te...F ChB and their interactions were characterized using various NMR techniques. The energy of Te...F ChB was estimated to be 3-11 kJ mol(-1) depending on the substituents.
Article
Chemistry, Inorganic & Nuclear
Adnana Zaulet, Miquel Nuez, Reijo Sillanpaa, Francesc Teixidor, Clara Vinas
Summary: This work isolates the cobaltabis(dicarbollide) salts of biocompatible divalent cations of biological importance for potential applications in biology and materials science. The study reports the preparation of Ca2+, Mg2+ and Fe2+ salts with anionic iodinated nido-[C2B9H12](-) and cobaltabis(dicarbollide), with different coordination behaviors in solvents. The Ca2+ and Mg2+ salts form aqua ions in the presence of water, while Fe2+ and Fe3+ display different coordination behaviors in acetone.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Maxime Beau, Olivier Jeannin, Marc Fourmigue, Pascale Auban-Senzier, Frederic Barriere, Ie-Rang Jeon
Summary: Chalcogen bonding interactions were investigated in two new -SeMe substituted tetrathiafulvalene derivatives, demonstrating efficient sigma-hole activation of selenium through redox-active substituents.
Article
Chemistry, Physical
Mahmoud A. A. Ibrahim, Mohammed N. Shehata, Mahmoud E. S. Soliman, Mahmoud F. Moustafa, H. R. Abd El-Mageed, Nayra A. M. Moussa
Summary: The energetic findings revealed a preferential tendency of selenium-bearing molecules to engage in chalcogen interactions, with type IV interactions showing the most favorable negative binding energies in like complexes. The QTAIM analysis provided insights into the primary BCP through chalcogen interactions, while SAPT-EDA highlighted the dominance of dispersion forces in these interactions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Steve Scheiner
Summary: The chalcogen Y atom in thiophene and its derivatives can interact with another Y atom within the homodimer in different geometries, including a perpendicular T-shaped dimer and two symmetric Y center dot center dot center dot Y interactions. The strength of the Y center dot center dot center dot Y interactions is effectively doubled due to the simultaneous charge transfer in both directions. These geometries differ from what would be expected based solely on the electrostatic potentials.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Physical
Steve Scheiner
Summary: The chalcogen Y atom in the aromatic ring of thiophene and its derivatives YC4H4 (Y = S, Se, Te) can interact in multiple ways with other Y atoms within the homodimer. The preferred geometry involves perpendicular orientation of the two rings in a T-shaped dimer, where the Y atom forms a chalcogen bond (ChB) by accepting electron density from the π-system of the other unit. In addition to this, there are two other geometries where the Y atoms engage in ChB with each other. However, in these cases, the interaction is better described as a pair of symmetrically equivalent Y-Y interactions where charge is transferred in both directions, doubling the bond strength.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Article
Chemistry, Inorganic & Nuclear
Ines Bennour, M. Nuria Ramos, Miquel Nuez-Martinez, Jewel Ann Maria Xavier, Ana B. Buades, Reijo Sillanpaa, Francesc Teixidor, Duane Choquesillo-Lazarte, Isabel Romero, Margarita Martinez-Medina, Clara Vinas
Summary: In this study, the synthesis and characterization of two small molecules were reported. One of the compounds showed antimicrobial activity against Candida species and Gram-positive/negative bacteria with low toxicity, making it a potential candidate for antimicrobial therapy. Moreover, the influence of compound structure and environmental factors on antimicrobial properties was investigated.
DALTON TRANSACTIONS
(2022)
Article
Biochemistry & Molecular Biology
Kyrill Yu. Suponitsky, Sergey A. A. Anufriev, Igor B. B. Sivaev
Summary: The crystal structures of two isomeric triiodo derivatives of ortho-carborane were determined, showing different bonding patterns of iodine atoms with the carborane cage. The existence of dihalogen bonds and halogen bonds were observed in the structures. Comparison with the brominated derivative revealed similarities and differences in the bonding interactions.
Article
Chemistry, Organic
Kyrill Yu. Suponitsky, Kirill V. V. Strizhenko
Summary: The title compound was synthesized and characterized by IR and NMR spectroscopy and single crystal X-ray diffraction. The crystal packing analysis of the compound and its nitro analog revealed that the CN group is lighter in mass, less dense, and participates in intermolecular bonding to a lesser extent compared to the NO2 group. As a result, the cyano compound has a lower density and a looser crystal packing than the nitro analog.
Article
Chemistry, Inorganic & Nuclear
Igor B. Sivaev, Sergey A. Anufriev, Akim V. Shmalko
Summary: Based on the data of 1H NMR spectra, the effect of various substituents at boron atoms in different positions of the ortho-carborane cage on its CH-acidity and the electron-withdrawing effect upon substitution at the carbon atom is discussed. It is found that the introduction of chlorine atoms slightly reduces the CH-acidity, whereas the introduction of bromine and iodine atoms significantly increases the CH-acidity compared to the parent orthocarborane. The introduction of halogen atoms to the boron atoms bound to both carbon atoms leads to a significant increase in the CH-acidity, regardless of halogen electronegativity. However, in the case of polychlorinated derivatives of ortho-carborane, the total effect of the substituent covers the decrease in CH-acidity when the first halogen atoms are introduced into specific positions. The introduction of alkyl substituents reduces the CH-acidity, while the introduction of aryl substituents has the opposite effect.
INORGANICA CHIMICA ACTA
(2023)
Article
Biochemistry & Molecular Biology
Pavel S. Gribov, Natalia N. Kondakova, Natalia N. Il'icheva, Evgenia R. Stepanova, Anatoly P. Denisyuk, Vladimir A. Sizov, Varvara D. Dotsenko, Dmitry B. Vinogradov, Pavel V. Bulatov, Valery P. Sinditskii, Kyrill Yu. Suponitsky, Mikhail M. Il'in, Mukhamed L. Keshtov, Aleksei B. Sheremetev
Summary: In this study, a method for synthesizing energetic polymers containing furazan, 1,2,3-triazole rings, and nitramine groups in the polymer chain was developed using dialkyne and diazide comonomers with explosophoric groups. The method is solvent- and catalyst-free, simple, and effective, making it a promising tool for the synthesis of energetic polymers. The resulting polymer was fully characterized and showed potential as a binder base for energetic materials, surpassing nitrocellulose in several properties.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Chemistry, Inorganic & Nuclear
Dmitriy K. Semyonov, Georgii K. Slushko, Marina Yu. Stogniy, Sergey A. Anufriev, Ivan A. Godovikov, Kyrill Yu. Suponitsky, Vladimir I. Bregadze, Igor B. Sivaev
Summary: The reactions of nickel(II) phosphine complexes [(dppe)NiCl2], [(MePh2P)2NiCl2] and [(Ph3P)2NiCl2] with C-substituted nido-carboranes [7-R-nido-7,8-C2B9H11]- were investigated. Different reactions were observed depending on the specific combination of reactants. Overall, the findings highlight the impact of steric interactions on the formation of nickelacarboranes.
Article
Chemistry, Multidisciplinary
K. E. Erdelyi, A. A. Antonets, O. B. Zhidkova, A. A. Druzina, A. A. Nazarov, S. V. Timofeev, I. B. Sivaev, V. I. Bregadze
Summary: Boron-containing conjugates of cholesterol were synthesized via copper(I)-catalyzed 1,3-dipolar [3+2] cycloaddition reactions. The antiproliferative activity of the conjugates was evaluated against various human cell lines, showing low toxicity and potential for cancer treatment.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Inorganic & Nuclear
Dmitriy K. Semyonov, Marina Yu. Stogniy, Kyrill Yu. Suponitsky, Igor B. Sivaev
Summary: New carboranyl thioethers were synthesized using the alkylation of the trimethylammonium salt of 1-mercapto-ortho-carborane with 1-bromo-2-methoxyethane and 1-bromo-3-methoxypropane. The deboronation of these thioethers with cesium fluoride yielded the corresponding nido-carboranes. The reactions of the nido-carboranes with various nickel(II) phosphine complexes resulted in the synthesis of nickelacarboranes.
Article
Biochemistry & Molecular Biology
Dmitriy K. Semyonov, Marina Yu. Stogniy, Sergey A. Anufriev, Sergey V. Timofeev, Kyrill Yu. Suponitsky, Igor B. Sivaev
Summary: A series of C- and B-substituted nido-carborane derivatives with a pendant pyridyl group were synthesized and used as ligands for the complexation reactions with nickel(II) and palladium(II) chlorides, forming six new metallacomplexes. The structures of these complexes were determined using single crystal X-ray diffraction.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Medicine, Research & Experimental
Satoshi Okada, Kai Nishimura, Qarri Ainaya, Kouichi Shiraishi, Sergey A. Anufriev, Igor B. Sivaev, Yoshinori Sakurai, Minoru Suzuki, Masayuki Yokoyama, Hiroyuki Nakamura
Summary: In this study, a gadolinium-boron-conjugated albumin (Gd-MID-BSA) was developed for MRI-guided neutron capture therapy. The accumulation of Gd-MID-BSA in tumors was confirmed by MRI and biodistribution analysis. The concentration ratios of boron and gadolinium in tumors satisfied the requirements for boron neutron capture therapy (BNCT) and gadolinium neutron capture therapy (GdNCT). The conjugation of gadolinium and boron in the albumin molecule enhanced the therapeutic effect of BNCT and showed potential as a promising treatment for malignant tumors.
MOLECULAR PHARMACEUTICS
(2023)
Article
Biochemistry & Molecular Biology
Anna A. Druzina, Nadezhda V. Dudarova, Ivan V. Ananyev, Anastasia A. Antonets, Dmitry N. Kaluzhny, Alexey A. Nazarov, Igor B. Sivaev, Vladimir I. Bregadze
Summary: The synthesis of the first conjugates of acridine with cobalt bis(dicarbollide) was reported. A novel 9-azido derivative of acridine was prepared and its solid-state molecular structure was determined. The obtained conjugates showed weak binding with DNA, but demonstrated potential for the development of new agents for boron neutron capture therapy (BNCT).
Article
Chemistry, Multidisciplinary
A. A. Druzina, N. V. Dudarova, I. B. Sivaev, V. I. Bregadze
Summary: A new azidoethylaminoacridine compound was synthesized and boron-containing acridine conjugates were obtained through a specific reaction. These compounds have potential applications as DNA intercalators for boron neutron capture therapy.
RUSSIAN CHEMICAL BULLETIN
(2023)
Article
Chemistry, Inorganic & Nuclear
A. M. Zimina, T. V. Kolpakova, S. A. Anufriev, E. I. Zueva, N. V. Somov, I. B. Sivaev, I. D. Grishin
Summary: The reaction of 9-iodo-ortho-carborane with n-butylmagnesium bromide produces 9-n-butyl-ortho-carborane. Further reaction of this compound with alkali in boiling ethanol yields a new nido-carborane [5-Bu-7,8-C2B9H11](-) (I) with a n-butyl substituent. Subsequent reaction of compound I with RuCl2(PPh3)(Ph2P(CH2)(4)PPh2) leads to the formation of a ruthenium(IV) closo complex 3,3-(Ph2P(CH2)(4)PPh2)-3-H-3-Cl-9-Bu-closo-3,1,2-RuC2B9H10 (II) characterized by 2D NMR spectroscopy. Heating compound II with carbon tetrachloride results in the formation of the 17-electron complex 3,3-(Ph2P(CH2)(4)PPh2)-3-Cl-9-Bu-closo-3,1,2-RuC2B9H10, and the structure of this complex is determined using X-ray diffraction.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
(2023)
Article
Materials Science, Multidisciplinary
Nikita V. Muravyev, Igor N. Melnikov, Dmitry K. Pronkin, Dmitry L. Lipilin, Kyrill Yu. Suponitsky, Aleksei B. Sheremetev, Igor L. Dalinger
Summary: This article reports a high-energy mesoionic liquid, 3-methylazasydnone, that can function as both a monopropellant and in bipropellant systems. It has high density, moderate volatility, good thermal stability, and is insensitive to impact. The computed combustion performance of the liquid propellant is superior to a benchmark energetic ionic liquid. Overall, 3-methylazasydnone is a promising functional material for green liquid mono- and bipropellants.
ACS MATERIALS LETTERS
(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)
