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, Inorganic & Nuclear
Toby J. Blundell, Jordan R. Lopez, Kathryn Sneade, John D. Wallis, Hiroki Akutsu, Yasuhiro Nakazawa, Simon J. Coles, Claire Wilson, Lee Martin
Summary: This study reports the first examples of radical-cation salts of BEDT-TTF with spiroborate anions [B(mandelate)(2)](-) and [B(2-chloromandelate)(2)](-), synthesized from enantiopure or racemic bidentate mandelate or chloromandelate ligands. In the salts prepared using enantiopure ligands, only one diastereoisomer of the spiroborate anion is incorporated with the same stereochemistry as the ligand. For the racemic salts, one racemic pair of spiroborate anions containing an R and an S mandelate ligand is incorporated. Helical crystals were obtained when using spiroborate anions with enantiopure ligands in certain solvents. Electric and magnetic properties, as well as band structure calculations, are reported.
DALTON TRANSACTIONS
(2022)
Article
Biochemistry & Molecular Biology
Ekaterina Bogdanova, Marina Yu Stogniy, Kyrill Yu Suponitsky, Igor B. Sivaev, Vladimir Bregadze
Summary: A series of novel cobalt bis(dicarbollide) based amidines were synthesized by adding primary and secondary amines to a specific compound, leading to different isomer mixtures when reacting with primary vs. secondary amines. Crystal structures of these compounds were determined by X-ray diffraction.
Article
Crystallography
Denis M. Chudak, Olga N. Kazheva, Irina D. Kosenko, Gennady Shilov, Igor B. Sivaev, Georgy G. Abashev, Elena Shklyaeva, Lev Buravov, Dmitry N. Pevtsov, Tatiana N. Starodub, Vladimir Bregadze, Oleg A. Dyachenko
Summary: New radical-cation salts based on TMTTF and TMsTSF with different metallacarborane anions were synthesized, with the third salt being a narrow-gap semiconductor.
Article
Materials Science, Multidisciplinary
Flavia Pop, Cecile Meziere, Magali Allain, Pascale Auban-Senzier, Naoya Tajima, Daichi Hirobe, Hiroshi M. Yamamoto, Enric Canadell, Narcis Avarvari
Summary: Electrocrystallization of tetramethyl-bis(ethylenedithio)-tetrathiafulvalene resulted in a series of isostructural enantiopure radical cation salts. These salts exhibited good semiconducting behavior with relatively high room temperature conductivity and potential as candidates for Dirac cone materials. Further analysis of their electronic structure suggests a Mott insulator behavior and preliminary field effect transistor measurements provided insight into their conducting properties.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Chemistry, Analytical
Tatiana Shishkanova, Alla Sinica
Summary: A cobalt bis(dicarbollide) derivative deposited onto the surface of a graphite electrode through an electrochemically oxidized o-phenylenediamine unit (pCB-oPD) is proposed for the detection of catecholamine metabolites, namely homovanillic acid (HVA) and vanillylmandelic acid (VMA). The set of electrochemical techniques makes it possible to evaluate the options of the individual and simultaneous detection of metabolites.
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Hadi Hachem, HengBo Cui, Reizo Kato, Pere Alemany, Enric Canadell, Olivier Jeannin, Marc Fourmigue, Dominique Lorcy
Summary: Highly conducting, mixed-valence, multi-component nickel bis-(diselenolene) salts were obtained by electrocrystallization. Depending on the counter ion used, the salts showed different stoichiometries of 1:2 and 1:3. This is a rare example of mixed-valence conducting salts of nickel diselenolene complexes, which usually form single component neutral species. The transport measurements under high pressure and band structure calculations confirmed the semiconducting and quasi metallic characters of the salts.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Hiroki Akutsu, Scott S. Turner, Yasuhiro Nakazawa
Summary: This compound exhibits a phase transition at 160 K, forming a crucial structure with 1D Heisenberg antiferromagnetic behavior, while further cooling below 140 K leads to the formation of a spin ladder system.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Biochemistry & Molecular Biology
Lyubov G. Dezhenkova, Anna A. Druzina, Yulia L. Volodina, Nadezhda Dudarova, Natalia A. Nekrasova, Olga B. Zhidkova, Mikhail A. Grin, Vladimir Bregadze
Summary: Novel cobalt bis(dicarbollide)-curcumin conjugates were synthesized and found to be non-cytotoxic against tumor and normal cells. Flow cytometry analysis showed that these conjugates entered the cells in a time-dependent manner.
Article
Chemistry, Multidisciplinary
Naoya Kinoshita, Takashi Shirahata, Toshio Naito, Yohji Misaki
Summary: Synthesis and X-ray structure analysis of TSF-based donors substituted with the meso-dimethylethylenedithio group were successfully performed. The donor molecules in (meso-DM-BETS)(2)X formed a dimerized face-to-face p-stack, with a packing pattern classified as ss-type. Tight-binding band calculation suggested that the meso-DM-BETS salts have a two-dimensional Fermi surface and wide bandwidth. Both salts exhibited metallic conductivities down to low temperatures with sigma(r.t.) = 45-46 S cm(-1).
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
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
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.
Article
Materials Science, Multidisciplinary
Yann Le Gal, HengBo Cui, Pere Alemany, Enric Canadell, Reizo Kato, Thierry Roisnel, Vincent Dorcet, Marc Fourmigue, Dominique Lorcy
Summary: Electrocrystallization of an original gold bis(diselenolene) complex yields a mixed-valence 1:2 salt with rare charge alternation, containing both cis and trans isomers of the gold complex in the conducting layers. The salt is semiconducting at room temperature but turns metallic under pressure, making it the first fully characterized 1:2 mixed-valence gold complex with potential for highly conducting solids.
JOURNAL OF MATERIALS CHEMISTRY C
(2021)
Article
Chemistry, Physical
Kane Jacob, Christophe Faulmann, Dominique de Caro, Lydie Valade
Summary: Nanoparticles of (BETS)(2)FeCl4 were successfully obtained using electrochemical oxidation and a growth controlling agent, with sizes ranging from 10-40 nm and exhibiting a kappa-type structure. The current-voltage characteristic recorded on an individual nanoparticle aggregate fitted with a Shockley diode model.
Article
Chemistry, Physical
Fabio Montisci, Arianna Lanza, Martin Fisch, Camille Sonneville, Yan Geng, Christian Reber, Silvio Decurtins, Shi-Xia Liu, Piero Macchi
Summary: This study focuses on the effect of compression and cooling on the stereolectronic properties of TTF-BTD molecule and predicts the formation of a new phase under high pressure.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
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.
Review
Chemistry, Inorganic & Nuclear
Marina Yu. Stogniy, Sergey A. Anufriev, Igor B. Sivaev
Summary: This review summarizes data on the main types of charge-compensated nido-carborane derivatives, which have increased stability compared to organic analogs. The stability is attributed to the stabilizing electron-donor action of the boron cage. The charge-compensated derivatives are discussed based on the type of heteroatom bonded to a boron atom.
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
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.
Review
Chemistry, Multidisciplinary
Igor B. B. Sivaev
Summary: This review aims to compile the literature data on the synthesis and properties of icosahedral carborane derivatives, specifically focusing on the attachment of exo-polyhedral three- and four-coordinated boron substituents directly to the carborane cage through boron-carbon or boron-boron bonds. Various classes of compounds including carboranyl aryl boranes, boronic acids and their derivatives, boroles, diazaboroles, etc., are discussed. The review particularly highlights carborane-fused heterocycles containing boron atoms.
CHEMISTRY-SWITZERLAND
(2023)
Article
Chemistry, Inorganic & Nuclear
Varvara V. Avdeeva, Alexey S. Kubasov, Alexey V. Golubev, Sergey A. Anufriev, Igor B. Sivaev, Svetlana E. Nikiforova, Lyudmila V. Goeva, Elena A. Malinina, Nikolay T. Kuznetsov
Summary: Reactions of [B11H11]2- with copper(I) and silver(I) complexes [(Ph3P)3MX] (M = Cu, X = Cl; M = Ag, X = NO3) led to the formation of metallaboranes (Bu4N)3[commo-M(B11H11)2] instead of M-H-B complexes. The crystal structure of (Bu4N)3[Ag(B11H11)2] was determined using single-crystal X-ray diffraction. Hirschfeld surface analysis and DFT calculations were conducted for both metallaboranes [M (B11H11)2]3- (M = Cu, Ag).
INORGANICA CHIMICA ACTA
(2023)
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)
Review
Chemistry, Inorganic & Nuclear
Yu. N. Las'kova, A. A. Serdyukov, I. B. Sivaev
Summary: This article summarizes the synthesis methods, properties, and application fields of various boron-containing coumarin derivatives, with particular emphasis on derivatives with various polyhedral boron clusters as substituents, such as carboranes, metallacarboranes, and the closo-dodecaborate anion. Derivatives of coumarin with simple organoboron compounds, boronic acids and their esters, are also considered.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
(2023)
Review
Chemistry, Physical
Varvara V. Avdeeva, Svetlana E. Nikiforova, Elena A. Malinina, Igor B. Sivaev, Nikolay T. Kuznetsov
Summary: In this article, composites and materials prepared from boron hydride cluster compounds are presented. The utilization of these materials as boron protective coatings, as well as their applications in synthesizing boron carbide, boron nitride, metal borides, metal-containing composites, and neutron shielding materials, are discussed.