共查询到20条相似文献,搜索用时 15 毫秒
1.
Ekaterina V. Bogdanova Marina Yu. Stogniy Kyrill Yu. Suponitsky Igor B. Sivaev Vladimir I. Bregadze 《Molecules (Basel, Switzerland)》2021,26(21)
A series of novel cobalt bis(dicarbollide) based amidines were synthesized by the nucleophilic addition of primary and secondary amines to highly activated B-N+≡C–R triple bond of the propionitrilium derivative [8-EtC≡N-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]. The reactions with primary amines result in the formation of mixtures of E and Z isomers of amidines, whereas the reactions with secondary amines lead selectively to the E-isomers. The crystal molecular structures of E-[8-EtC(NMe2)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)], E-[8-EtC(NEt2)=HN-3,3′-Co(1,2- C2B9H10)(1′,2′-C2B9H11)] and E-[8-EtC(NC5H10)=HN-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] were determined by single crystal X-ray diffraction. 相似文献
2.
Olga N. Kazheva Andrey V. Kravchenko Irina A. Lobanova Vladimir I. Bregadze Lev I. Buravov 《Journal of organometallic chemistry》2009,694(15):2336-450
New molecular conductors on the base of 8,8′-diiodo cobalt bis(dicarbollide) anion (TTF)[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (1), (BMDT-TTF)4[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (2) and (BEDT-TTF)2[8,8′-I2-3,3′-Co(1,2-C2B9H10)2] (3) were synthesized and their crystal structures and electrical conductivities were determined. All the radical cation salts prepared were found to be semiconductors. Some regularities in the crystal structures of the TTF-based radical cation salts with bis(dicarbollide) complexes of transition metals are discussed. 相似文献
3.
I. D. Kosenko I. A. Lobanova I. B. Sivaev P. V. Petrovskii V. I. Bregadze 《Russian Chemical Bulletin》2011,60(11):2354-2358
A new approach to synthesis of hetero-substituted derivatives of cobalt bis(1,2-dicarbollide) was proposed. The approach involves stepwise introduction of functional groups into different dicarbollide ligands. Halogenation of the monohydroxy derivative [8-OH-3,3??-Co-(1,2-C2B9H10)(1??,2??-C2B9H11)]? gave the corresponding halogen hydroxy derivatives [8-OH-8??-X-3,3??-Co(1,2-C2B9H10)2]? (X = Cl, Br, and I). Reactions of 8,8??-??-iodonium-3-commo-cobaltbis(1,2-dicarba-closo-dodecaborate) [8,8??-I-3,3??-Co(1,2-C2B9H10)2] with chloroform and 1,2-dibromoethane yielded the mixed halides [8-Y-8??-I-3,3??-Co(1,2-C2B9H10)2]? (Y = Cl and Br). 相似文献
4.
Igor B. Sivaev Zoya A. StarikovaStefan Sjöberg Vladimir I. Bregadze 《Journal of organometallic chemistry》2002,649(1):1-8
A series of various functional derivatives of the cobalt bis(1,2-dicarbollide) anion [8-XCH2CH2OCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]− (X=OH, NH2, and CH(NH2)COOH) were prepared by the ring-opening reactions of [8-O(CH2CH2)2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] with different nucleophiles followed by functional group interconversion reactions. Acidic hydrolysis of [8-NCCH2CH2OCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]− resulted in the shorter-chain alcohol [8-HOCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)]−. Structures of (Bu4N)[8-AcNHC(COOEt)2CH2CH2OCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] and [8-(1-C5H5N)CH2CH2OCH2CH2O-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] were determined by the single crystal X-ray diffraction method. Perspectives of application of functionalized cobalt bis(1,2-dicarbolide) derivatives in nuclear medicine are discussed. 相似文献
5.
Olga N. Kazheva Andrey V. Kravchenko Igor B. Sivaev Irina A. Lobanova Lev I. Buravov 《Journal of organometallic chemistry》2007,692(22):5033-5043
New radical cation salts (BEDT-TTF)2[3,3′-Co(1,2-C2B9H11)2] (1), (BEDT-TTF)2[8-I-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] (2), (BMDT-TTF)[3,3′-Co(1,2-C2B9H11)2] (3) and (TMTSF)2[3,3′-Fe(1,2-C2B9H11)2] (4) were synthesized and their crystal structures and electrical conductivities were determined. Compound 4 is isostructural to the earlier reported Co analogue. All the radical cation salts synthesized are semiconductors. 相似文献
6.
Olga N. Kazheva Grigorii G. Alexandrov Andrey V. Kravchenko Igor B. Sivaev Vladimir I. Bregadze 《Journal of organometallic chemistry》2006,691(20):4225-4233
New radical cation salts (TMTSF)2[3,3′-Co(1,2-C2B9H11)2] (1), (TTF)[3,3′-Co(1,2-C2B9H11)2] (2) and (ET)[3,3′-Co(1,2-C2B9H11)2] (3) were synthesized and their crystal structures and electrical conductivities were determined. Compound 1 has layered structure with conducting stacks of the TMTSF cations, whereas compounds 2 and 3 contain separated pairs of fulvalenium cations. Conductivity of crystals 1 at room temperature was found to be 15 Ohm−1 cm−1, that is the maximum value found for fulvalenium metallacarborane salts. 相似文献
7.
O. N. Kazheva G. G. Aleksandrov A. V. Kravchenko V. A. Starodub G. G. Zhigareva I. B. Sivaev V. I. Bregadze L. I. Buravov L. V. Titov O. A. D’yachenko 《Russian Chemical Bulletin》2010,59(6):1137-1144
The radical cation salts of tetrathiafulvalene (TTF) and bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) with iodo derivatives
of cobalt bis(dicarbollide), (TTF)[9,9′,12,12′-I4-3,3′-Co(1,2-C2B9H9)2] and (BEDT-TTF)[9,9′(12′)-I2-3,3′-Co(1,2-C2B9H10)2], respectively, were synthesized and their crystal structures were determined. The introduction of iodine atoms into the
lower rim of the dicarbollide ligands, unlike the substitution at the upper rim, leads to insignificant changes in the crystal
structure and the conductivity of the radical cation salts compared to the analogous salts based on unsubstituted cobalt bis(dicarbollide). 相似文献
8.
D. A. Rudakov V. L. Shirokii V. A. Knizhnikov A. V. Bazhanov E. I. Vecher N. A. Maier V. I. Potkin A. N. Ryabtsev P. V. Petrovskii I. B. Sivaev V. I. Bregadze I. L. Eremenko 《Russian Chemical Bulletin》2004,53(11):2554-2557
A convenient electrochemical method for the synthesis of 8,8-dihalogen derivatives of bis(1,2-dicarbollyl)cobalt(III) anion [8,8X2-3,3-Co(1,2-C2B9H10)]– (X = Cl, Br, I) was developed. The method includes the electrolysis of a solution of alkaline metal halide and tetramethylammonium salt of bis(1,2-dicarbollyl)cobalt(III) in methanol at 50 °C in a one-compartment electrochemical cell with a nickel cathode and platinum anode.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2448–2451, November, 2004. 相似文献
9.
《Mendeleev Communications》2022,32(3):354-356
The novel conjugates of cholesterol with cobalt – bis(dicarbollide) were synthesized by the ring-opening reactions of the cyclic oxonium derivatives of [3,3′-Co(C2B9H11)2]– with the OH group of cholesterol 2-hydroxyethyl ether. The compounds obtained were tested for toxicity to glioblastoma U-87 MG cells and human embryo fibroblasts FECH-15 cells 相似文献
10.
M. A. Grin R. A. Titeev O. M. Bakieva D. I. Brittal I. A. Lobanova I. B. Sivaev V. I. Bregadze A. F. Mironov 《Russian Chemical Bulletin》2008,57(10):2230-2232
A conjugate of the bacteriochlorophyll a derivative with the cobalt bis(dicarbollide) anion [3,3′-Co(1,2-C2B9H11)2]− was synthesized. 相似文献
11.
I. D. Kosenko I. A. Lobanova Z. A. Starikova V. I. Bregadze 《Russian Chemical Bulletin》2013,62(8):1914-1918
New hetero-substituted charge-compensated cobalt bis(1,2-dicarbollide) derivatives were synthesized by the reaction of 8,8′-μ-iodo-3-commo-3-cobalta-bis(1,2-dicarba-closo-dodecaborane) [8,8′-μ-I-3,3′-Co(1,2-C2B9H10)2] with 1,4-thioxane, pyridine N-oxide, and tetrahydropyran. X-ray diffraction studies showed that the 8′-iodo-8-(pyridiniumoxy)eucosahydro-1,1′,2,2′-tetracarba-3-commo-cobalta-closo-tricosaborate molecule has the gauche-conformation (the substituents are turned with respect to each other by 69.2°). The positive charge is predominantly localized on the N(Py) atom. 相似文献
12.
Ionic diamides composed of a N,N′-dialkyl diglycolyl complexing group and two cobalt bis(dicarbollide)(1−) anions were synthesized with the aim to develop efficient extraction agents for liquid-liquid extraction of polyvalent cations, i.e. lanthanides and actinides from high-level activity nuclear waste. Compounds of general formulation [{(N,N-(8-CH2-CH2O)2-1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Co)(N′,N′-R)NCOCH2}2O]Na2, where R = n-C4H9, n-C8H17, n-C12H25 and 1-C6H4-4-CH3 (1-4), were prepared and characterized by combination of 11B 1H, 13C NMR spectroscopy, ESI-MS, HPLC and other techniques. Effects of different nitrogen substitution in the structures of 1-4 on the extraction properties were tested. The study resulted in the observation that the compounds are significantly (2-3 orders in magnitude) more efficient extractants for Eu(III) and Am(III) than synergic mixtures of organic N,N′-tetra n-octyl diglycolic acid diamide (TODGA) and chlorinated cobalt bis(dicarbollide) at the same concentrations of both groups. Low polar mixtures of n-dodecane (D) and hexyl methyl ketone (HMK) can be applied as an auxiliary solvent for extraction, replacing thus the polar and less environmentally friendly nitro-, fluoro- and chloro- solvents used in the current dicarbollide liquid-liquid extraction process. 相似文献
13.
Bohumír Grüner Magdaléna Kví?alová Václav Šícha Mária Lu?aníková 《Journal of organometallic chemistry》2009,694(11):1678-1264
New boron substituted cobalta bis(dicarbollide)(1-) ion (1) derivatives of formula [(8,8′-(RPhP(O)(CH2)nC(O)N) < (1,2-C2B9H10)2-3,3′-Co]− (R = Ph or C8H17, n = 1, 3a, 3b; R = Ph, n = 2, 3c), [(8-(Ph2P(O)CH2C(O)NR)(1,2-C2B9H10))(1′,2′-C2B9H11)-3,3′-Co]− (R = H, C2H5, CH2C6H5, 5a-c) and [(8-(2RPhP(O)CH2C(O)N(1R)CH2-1,2-C2B9H10))(8′-CH3O-1′,2′-C2B9H10)-3,3′-Co]− (1R = Benzyl, 2R = Ph or C8H17, 7a,b) were prepared with the aim to develop a new class of efficient extraction agents for partitioning of polyvalent f-block elements, i.e. lanthanides and actinides from high-level activity nuclear waste. The anionic ligands were characterized by multinuclear NMR spectroscopy and MS, the structures of Cs3a and the calcium complex of 7a were determined by X-ray diffraction analysis. The crystallographic study of the Cs3a proved a formation of linear chains in the structure, where the metal cation is coordinated by oxygen atoms of the CMPO terminal groups. The X-ray structure of the Ca2+ complex of the ionic ligand 7a proved a 1:3 metal to ligand ratio. Presented also is the X-ray structure of the starting ammonium compound 6 used in the synthesis of 7a and 7b. With exception of 5c, these anionic ligands are of high extraction efficiency, the highest being found for 7a in low polar solvent mixture hexyl methyl ketone-dodecane 1:1. These properties qualify some of these derivatives for possible technological applications. 相似文献
14.
Clve D. Mboyi Ons Amamou Paul Fleurat-Lessard Julien Roger Hlne Cattey Charles H. Devillers Michel Meyer Taoufik Boubaker Jean-Cyrille Hierso 《Molecules (Basel, Switzerland)》2021,26(9)
The carbon-carbon cross-coupling of phenyl s-tetrazine (Tz) units at their ortho-phenyl positions allows the formation of constrained bis(tetrazines) with original tweezer structures. In these compounds, the face-to-face positioning of the central tetrazine cores is reinforced by π-stacking of the electron-poor nitrogen-containing heteroaromatic moieties. The resulting tetra-aromatic structure can be used as a weak coordinating ligand with cationic silver. This coordination generates a set of bis(tetrazine)-silver(I) coordination complexes tolerating a large variety of counter anions of various geometries, namely, PF6−, BF4−, SbF6−, ClO4−, NTf2−, and OTf−. These compounds were characterized in the solid state by single-crystal X-ray diffraction (XRD) and diffuse reflectance spectroscopy, and in solution by 1H-NMR, mass spectrometry, electroanalysis, and UV-visible absorption spectrophotometry. The X-ray crystal structure of complexes {[Ag(3)][PF6]}∞ (4) and {[Ag(3)][SbF6]}∞ (6), where 3 is 3,3′-[(1,1′-biphenyl)-2,2′-diyl]-6,6′-bis(phenyl)-1,2,4,5-tetrazine, revealed the formation of 1D polymeric chains, characterized by an evolution to a large opening of the original tweezer and a coordination of silver(I) via two chelating nitrogen atom and some C=C π-interactions. Electrochemical and UV spectroscopic properties of the original tweezer and of the corresponding silver complexes are reported and compared. 1H-NMR titrations with AgNTf2 allowed the determination of the stoichiometry and apparent stability of two solution species, namely [Ag(3)]+ and [Ag(3)2]2+, that formed in CDCl3/CD3OD 2:1 v/v mixtures. 相似文献
15.
Anna A. Druzina Olga B. Zhidkova Nadezhda V. Dudarova Irina D. Kosenko Ivan V. Ananyev Sergey V. Timofeev Vladimir I. Bregadze 《Molecules (Basel, Switzerland)》2021,26(3)
Novel zwitter-ionic nido-carboranyl azide 9-N3(CH2)3Me2N-nido-7,8-C2B9H11 was prepared by the reaction of 9-Cl(CH2)3Me2N-nido-7,8-C2B9H11 with NaN3. The solid-state molecular structure of nido-carboranyl azide was determined by single-crystal X-ray diffraction. 9-N3(CH2)3Me2N-nido-7,8-C2B9H11 was used for the copper(I)-catalyzed azide-alkyne cycloaddition with phenylacetylene, alkynyl-3β-cholesterol and cobalt/iron bis(dicarbollide) terminal alkynes to form the target 1,2,3-triazoles. The nido-carborane-cholesterol conjugate 9-3β-Chol-O(CH2)C-CH-N3(CH2)3Me2N-nido-7,8-C2B9H11 with charge-compensated group in a linker can be used as a precursor for preparation of liposomes for Boron Neutron Capture Therapy (BNCT). A series of novel zwitter-ionic boron-enriched cluster compounds bearing a 1,2,3-triazol-metallacarborane-carborane conjugated system was synthesized. Prepared conjugates contain a large amount of boron atom in the biomolecule and potentially can be used for BNCT. 相似文献
16.
E. V. Balagurova I. V. Pisareva I. A. Godovikov A. F. Smol’yakov F. M. Dolgushin I. T. Chizhevsky 《Russian Chemical Bulletin》2013,62(2):548-553
Zwitterionic 4,8,8′-exo-{Ph3PCu}-4,8,8′-(μ-H)3-commo-3,3′-Co(1,2-C2B9H9)-(1′,2′-C2B9H10) and ionic [(PPh3)3Cu][commo-3,3′-Co(1,2-C2B9H11)2 complexes were synthesized in moderate yields by the reaction of anionic commo-complex [Cs][commo-3,3′-Co-(1,2-C2B9H11)2]) in a CH2Cl2 solution with anhydrous CuCl2 or CuCl in the presence of PPh3. The complexes were also synthesized by alternative methods and characterized by NMR and X-ray diffraction methods. 相似文献
17.
M. Bubeníková P. Selucky J. Rais B. Grüner P. ?vec 《Journal of Radioanalytical and Nuclear Chemistry》2012,293(1):403-408
The separation of minor actinides from high level liquid waste (HLLW) belongs to the principal challenges in current nuclear treatment. A derivative based on two cobalt bis(dicarbollide) (1?) ions covalently bound to the N,N??-di-n-octyl diglycolyl amide platform via diethyleneglycol chain with the formula {[(N,N??-(8-(OCH2 CH2)2-1,2-C2B9H10)(1??,2??-C2B9H11)-3,3??-Co)(N,N??-n-C8H17)NCOCH2]2O}Na2 (TODGA-COSAN), dissolved in low polar mixture of hexyl methyl ketone and n-dodecane, was used as an extractant for efficient Am(III)/Eu(III) separation from PUREX HLLW. Am(III) could be selectively stripped from loaded organic phase by using a stripping agent composed from 0.05?M DTPA and 1?M citric acid as a buffer and 1?M NaNO3 at pH?3.0. Separation factor between europium and americium of 13 was achieved. The europium remaining in the organic phase could be consecutively effectively stripped by using solution of ammonium citrate or ammonium citrate with ammonium DTPA at pH~7. 相似文献
18.
Erik Čižmár Daniela Šoltésová Olga N. Kazheva Grigorii G. Alexandrov Andrey V. Kravchenko Lyubov A. Chekulaeva Irina D. Kosenko Igor B. Sivaev Vladimir I. Bregadze Alexey V. Fedorchenko Vladimir A. Starodub Lev I. Buravov Oleg A. Dyachenko Alexander Feher 《Transition Metal Chemistry》2018,43(7):647-655
The synthesis of a radical-cation salt based on a derivative of tetrathiafulvalene, (ET)2[3,3′-Cr(1,2-C2B9H11)2] (ET?=?bis(ethylenedithio)tetrathiafulvalenium), was accomplished by electrochemical anodic oxidation of ET in the presence of (Me4N)[3,3´-Cr(1,2-C2B9H11)2] in the galvanostatic regime. An electric conductivity σ (293 K)?=?7 × 10?3 Ohm?1 cm?1 with semiconductor activation energy Ea???0.1 eV in the range of 127–300 K was observed. The crystal structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] was determined by X-ray diffraction at 173 K, revealing the presence of structural tetramers in radical-cation stacks. The magnetic properties of the complex were investigated in the temperature range 1.8–300 K using magnetometry and EPR, showing that the magnetic structure of (ET)2[3,3′-Cr(1,2-C2B9H11)2] consists of two independent magnetic subsystems. Cation radicals form a rectangular magnetic lattice in the ab-plane with significant antiferromagnetic exchange interactions. The chromium bis(dicarbollide) anions are characterized by unusually strong positive zero-field splitting of the Cr(III) ions, which was confirmed by ab initio calculations. 相似文献
19.
Lyubov G. Dezhenkova Anna A. Druzina Yulia L. Volodina Nadezhda V. Dudarova Natalia A. Nekrasova Olga B. Zhidkova Mikhail A. Grin Vladimir I. Bregadze 《Molecules (Basel, Switzerland)》2022,27(14)
A series of novel cobalt bis(dicarbollide)—curcumin conjugates were synthesized. Two conjugates were obtained through the nucleophilic ring-opening reaction of the 1,4-dioxane and tetrahydropyran derivatives of cobalt bis(dicarbollide) with the OH group of curcumin, and using two equiv. of the oxonium derivatives, two other conjugates containing two cobalt bis(dicarbollide) units per molecule were obtained. In contrast to curcumin, the conjugates obtained were found to be non-cytotoxic against both tumor and normal cell lines. The analysis of the intracellular accumulation of the conjugates by flow cytometry showed that all cobalt bis(dicarbollide)—curcumin conjugates entered HCT116 colorectal carcinoma cells in a time-dependent manner. New non-cytotoxic conjugates contain a large amount of boron atoms in the biomolecule and can potentially be used for further biological research into boron neutron capture therapy (BNCT). 相似文献