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1.
Marius Lupu Adnana Zaulet Prof. Dr. Francesc Teixidor Prof. Dr. Eliseo Ruiz Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6888-6897
The metallacarborane [3,3′‐Co(1,2‐closo‐C2B9H11)2]? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C2B9H7I4)2]? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed. 相似文献
2.
Quantum-chemical calculations of the geometry and energies of nine possible isomers of 12-vertex cobaltacarborane CpCoC2B9H11 (1) were carried out by the DFT method (PBEPBE/DGDZVP/DGA1). Thermodynamic stability of the isomers increases with increasing
distance between the carbon atoms in the cage and is virtually independent of the position of the CpCo vertex. The relative
stabilities of the 1,2,3-(17.57 kcal mol−1), 1,2,4-(3.72 kcal mol−1), and 1,2,9-isomers of 1 (0 kcal mol−1) are similar to the corresponding values for the ortho (17.61 kcal mol−1), meta (3.21 kcal mol−1), and para isomers (0 kcal mol−1) of carborane C2B10H12. The results of the present study confirm a close similarity of the CpCo and BH fragments in metallacarborane chemistry.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1557–1559, July, 2005. 相似文献
3.
Tania Merhi Alban Jonchère Dr. Luc Girard Dr. Olivier Diat Miquel Nuez Prof. Clara Viñas Dr. Pierre Bauduin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(61):13935-13947
Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C2B9H11)2]−, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations. 相似文献
4.
Carborane Substituents Promote Direct Electrophilic Insertion over Reduction–Metalation Reactions
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Dr. Wing Y. Man Dr. David Ellis Dr. Georgina M. Rosair Prof. Alan J. Welch 《Angewandte Chemie (International ed. in English)》2016,55(14):4596-4599
Two‐electron reduction of 1,1′‐bis(o‐carborane) followed by reaction with [Ru(η‐mes)Cl2]2 affords [8‐(1′‐1′,2′‐closo‐C2B10H11)‐4‐(η‐mes)‐4,1,8‐closo‐RuC2B10H11]. Subsequent two‐electron reduction of this species and treatment with [Ru(η‐arene)Cl2]2 results in the 14‐vertex/12‐vertex species [1‐(η‐mes)‐9‐(1′‐1′,2′‐closo‐C2B10H11)‐13‐(η‐arene)‐1,13,2,9‐closo‐Ru2C2B10H11] by direct electrophilic insertion, promoted by the carborane substituent in the 13‐vertex/12‐vertex precursor. When arene=mesitylene (mes), the diruthenium species is fluxional in solution at room temperature in a process that makes the metal–ligand fragments equivalent. A unique mechanism for this fluxionality is proposed and is shown to be fully consistent with the observed fluxionality or nonfluxionality of a series of previously reported 14‐vertex dicobaltacarboranes. 相似文献
5.
Olejniczak AB Plesek J Leśnikowski ZJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(1):311-318
A general approach to the synthesis of nucleoside conjugates between derivatives of thymidine (T), 2'-O-deoxycytidine (dC), 2'-O-deoxyadenosine (dA), and 2'-O-deoxyguanosine (dG), and metallacarborane complexes is described. Metallacarborane-nucleoside derivatives are prepared by reaction of the dioxane-metallacarborane adduct with a base-activated 3',5'-protected nucleoside. In the case of T and dG a mixture of regioisomers, which is easily separable by chromatographic methods, is obtained, thus yielding a series of modifications containing metallacarborane groups at the 2-O, 3-N, 4-O and 1-N, 2-N, 6-O locations, respectively; dC and dA are alkylated at the exo-amino function. The proposed methodology provides a route for the synthesis and study of nucleic acids modified with metallacarboranes at designated locations and a versatile approach to the incorporation of metals into DNA. 相似文献
6.
Tuning of Thermoresponsivity of a Poly(2‐alkyl‐2‐oxazoline) Block Copolymer by Interaction with Surface‐Active and Chaotropic Metallacarborane Anion
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Dr. Vladimír Ďorďovič Bart Verbraeken Prof. Richard Hogenboom Dr. Sami Kereïche Dr. Pavel Matějíček Dr. Mariusz Uchman 《化学:亚洲杂志》2018,13(7):838-845
Thermoresponsive nanoparticles based on the interaction of metallacarboranes, bulky chaotropic and surface‐active anions, and poly(2‐alkyl‐2‐oxazoline) block copolymers were prepared. Recently, the great potential of metallacarboranes have been recognized in biomedicine and many delivery nanosystems have been proposed. However, none of them are thermoresponsive. Therefore, a thermoresponsive block copolymer, poly(2‐methyl‐2‐oxazoline)‐block‐poly(2‐n‐propyl‐2‐oxazoline) (PMeOx–PPrOx), was synthesized to encapsulate metallacarboranes. Light scattering, NMR spectroscopy, isothermal titration calorimetry, and cryogenic TEM were used to characterize all solutions of the formed nanoparticles. The cloud‐point temperature (TCP) of the block copolymer was observed at 30 °C and polymeric micelles formed above this temperature. Cobalt bis(dicarbollide) anion (COSAN) interacts with both polymeric segments. Depending on the COSAN concentration, this affinity influenced the phase transition of the thermoresponsive PPrOx block. The TCP shifted to lower values at a lower COSAN content. At higher COSAN concentrations, the hybrid nanoparticles are fragmented into relatively small pieces. This system is also thermoresponsive, whereby an increase in temperature leads to higher polymer mobility and COSAN release. 相似文献
7.
A. R. Kudinov M. I. Rybinskaya D. S. Perekalin V. I. Meshcheryakov Yu. A. Zhuravlev P. V. Petrovskii A. A. Korlyukov D. G. Golovanov K. A. Lyssenko 《Russian Chemical Bulletin》2004,53(9):1958-1962
The structures of the metallacarborane cations [(-9-Me2S-7,8-C2B9H10)Ni(-Cp)Ni(-9-Me2S-7,8-C2B9H10)]+ (2) and [Cp*Ru(Me2S-C2B9H10)RuCp*]+ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004. 相似文献
8.
Sergey A. Anufriev Igor B. Sivaev Hiroyuki Nakamura 《Phosphorus, sulfur, and silicon and the related elements》2020,195(11):910-917
AbstractTwo ways of synthesis of theragnostic compounds for Gd-guided boron neutron capture therapy of cancer are proposed. The first way is based on modification of DO3A ligand, which a capable to form stable complexes with gadolinium, with attachment of boron-containing moieties and additional functional groups which can be used for conjugation with various biomacromolecules. The second way is based on the introduction of additional chelating groups into a boron-containing moiety—carborane-based ligand. It is expected that this will significantly improve the stability of the gadolinium bis(dicarbollide) complexes. 相似文献
9.
Kudinov A. R. Perekalin D. S. Petrovskii P. V. Grintselev-Knyazev G. V. 《Russian Chemical Bulletin》2002,51(10):1928-1930
The ruthenium arene complexes [(-arene)Ru(-9-SMe2-7,8-C2B9H10)]+ (arene = C6H6 (3a); arene = 1,3,5-C6H3Me3 (3b)) with the monoanionic carborane ligand were synthesized by the reactions of the [9-SMe2-7,8-C2B9H10]– anion with [(-arene)RuCl2]2. The structure of the compound [3a]BPh4 was established by single-crystal X-ray diffraction analysis. 相似文献
10.
A. R. Kudinov V. I. Meshcheryakov P. V. Petrovskii M. I. Rybinskaya 《Russian Chemical Bulletin》1999,48(1):176-178
Compounds (η-C5R5)Fe[η-9-(Me2S)-7,8-C2B9H10] (R=H, Me) and (η-C4Me4)Co[η-9-(Me2S)-7,8-C2B9H10] were synthesized by the reactions of Na[9-(Me2S)-7,8-C2B9H10] with complexes [(η-C5H5)Fe(MeCN)3]PF6, [(η-C5Me5)Fe(MeCN)3]BF4, and [(η-C4Me4)Co(MeCN)3]PF6, respectively.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179, January, 1999. 相似文献