共查询到20条相似文献,搜索用时 31 毫秒
1.
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
2.
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
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.
Jaromír Plešek Jan Machá?ek Ivana Císa?ová 《Journal of organometallic chemistry》2007,692(22):4801-4804
The synthesis of a new, paramagnetic closo-[(8-(-CH2CH2O)2-1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Fe]0 (3) is reported. This compound can serve as a versatile building block for construction of both anionic and zwitterionic derivatives, as exemplified by the synthesis of a series of compounds of general formula closo-[(8-X-(CH2CH2O)2-1,2-C2B9H10)(1′,2′-C2B9H11)-3,3′-Fe], bearing organic end groups (X = NC5H5 (4), (C6H5)3P (5), OH (6), and 2-O(1-CH3O-C6H4) (7)) attached to the cluster by a diethyleneglycol spacer. Molecular structures of 3, 4, 5 and 7 were determined by single-crystal X-ray diffraction analysis and by the long-time neglected method of paramagnetic, high field NMR (1H, 13C and 11B) spectroscopy. 相似文献
5.
Václav Šícha Bohumil Štíbr Bohumír Grüner Clara Viñas 《Journal of organometallic chemistry》2009,694(11):1599-281
The treatment of 1,2-, 1,7- and 1,12-carbaborane lithiated isomers with [3,3′-Co-8-(CH2CH2O)2-(1,2-C2B9H10)-(1′,2′-C2B9H11)] (1) at molar ratios 1:1 or 1:2 at room temperature in THF leads generally to the formation of a series of orange double-cluster mono and dianions. These were characterized by NMR and MS methods as [1′′-X-1′′,2′′-closo-C2B10H11]−, [2]−; [1′′-X-1′′,7′′-closo-C2B10H11]−, [3]− and [1′′-X-1′′,12′′-closo-C2B10H11], [4]− for the monoanions, whereas [1′′,2′′-X2-1′′,2′′-closo-C2B10H10]2−, [2]2−; [1′′,7′′-X2-1′′,7′′-closo-C2B10H10]2−, [3]2−; and [1′′,12′′-X2-1′′,12′′-closo-C2B10H10]2−, [4]2− for the dianions (where X = 3,3′-Co-8-(CH2CH2O)2-(1,2-C2B9H10)-1′,2′-(C2B9H11)). Moreover, these borane-cage subunits can be easily modified via attaching variable substituents onto cage carbon and boron vertices, which makes these compounds structurally flexible potential candidates for BNCT of cancer and HIV-PR inhibition. 相似文献
6.
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
7.
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
8.
Emilio José Juárez-Pérez 《Journal of organometallic chemistry》2009,694(11):1764-281
The recently reported crystal structure of [NMe4][1-SiMe2H-3,3′-Co(1,2-C2B9H10)(1′,2′-C2B9H11)] shows short contacts between the Si-H proton acceptor group and the Cc-H proton donor moiety in the dicarbollide ligand. These short contacts were studied within the framework of the Quantum Theory of Atoms in Molecules (QTAIM) at different levels of DFT theory (B3LYP/6-311(d,p) and BP86/TZ2P(+)) that shows the existence of a bifurcated Si-H?H-Cc dihydrogen bond. This paper presents the study of an experimental uncommon Si-H group playing as proton acceptor bond in a dihydrogen bond where hydrides like M-H (M, as metal transition), B-H or Al-H usually perform this role. Furthermore, this paper accounts with a new simple method to estimate bonding energies for closed-shell intramolecular interactions in the scheme of Voronoi charge population analysis and Coulomb′s Law. 相似文献
9.
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
10.
D. A. Loginov M. M. Vinogradov L. S. Shulpina A. V. Vologzhanina P. V. Petrovskii A. R. Kudinov 《Russian Chemical Bulletin》2007,56(10):2118-2120
The photochemical reaction of [(η5-C6H7)Fe(η-C6H6)]+ (1) with the [(η-9-SMe2-7,8-C2B9H10)]− anion followed by the treatment of the resulting ferracarborane (η-9-SMe2-7,8-C2B9H10)Fe(η5-C6H7) (2) with hydrochloric acid afforded the benzene complex [(η-9-SMe2-7,8-C2B9H10)Fe(η-C6H6)]+ (3). The reaction of cation 3 with ButNC produced the isonitrile complex [(η-9-SMe2-7,8-C2B9H10)Fe(tBuNC)3]+ (4). The structure of the complex [4]PF6 was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2046–2048, October, 2007. 相似文献
11.
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
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.
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
14.
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
15.
Yong Nie Jin-Ling MiaoChun-Hua Hu Hai-Yan ChenMan Sing Cheung Zhen-Yang LinMarkus Enders Walter Siebert 《Polyhedron》2012,31(1):607-613
The reaction of closo-[B10H10]2− with [PtCl2(PPh3)2] in MeOH at reflux affords the B-methoxy substituted 11-vertex nido-platinaborane compound [(PPh3)2PtB10H10-8-H0.5(OCH3)0.5-10-(OCH3)] (1) and the known species [(PPh3)2PtB10H11-8-(OCH3)] (2) and 1,6-(PPh3)2B10H8 (3). The same reaction under solvothermal condition gives the partially degraded diplatinaborane [(PPh3)2(μ-PPh2)Pt2B9H7-3,9,11-(OMe)3] (4) with a novel nido-Pt2B9H10 skeleton. The new metallaborane compounds have been characterized by spectroscopic methods and single-crystal X-ray analyses. In particular, computational/theoretical chemistry supports the ultimate structural confirmation of 4. The structures of these metallaboranes exhibit interesting intra- and/or intermolecular C-H?O hydrogen bonding interactions. 相似文献
16.
Maddalena Corsini Serena Losi Emanuela Grigiotti Fulvio Rossi Piero Zanello Alexander R. Kudinov Dmitry A. Loginov Mikhail M. Vinogradov Zoya A. Starikova 《Journal of Solid State Electrochemistry》2007,11(12):1643-1653
The reduction behavior of the isoelectronic complexes [CpMIII(η6-C6R6)]2+ (M=Rh, Ir; R=H, Me) and [(η-9-SMe2-7,8-C2B9H10)MIII(η6-C6R6)]2+ (M=Rh, Ir; C6R6 = C6H6, C6H5OMe, C6H3Me3) has been studied by cyclic voltammetry and controlled potential coulometry in acetonitrile and propylene carbonate at 253
and 298 K, respectively. The extent of chemical reversibility of the pertinent sequences Rh(III)/Rh(II)/Rh(I) and Ir(III)/Ir(I)
is highly dependent on both the nature of the solvent and the intrinsic electronic properties of the arene substituents. The
arene η6 coordination makes the derivatives in their lower oxidation states notably short lived, even if, in some cases, the use of
propylene carbonate improves their stability or causes the increase in their lifetimes before changing the arene coordination
from η6 to η4. Cations [(η-9-SMe2-7,8-C2B9H10)M(η6-C6R6)]2+ were obtained by the bromide abstraction from [(η-9-SMe2-7,8-C2B9H10)MBr2]2 with Ag+ in the presence of benzene and its derivatives. The structure of [(η-9-SMe2-7,8-C2B9H10)Ir(η6-C6H5OMe)](BF4)2 was determined by X-ray diffraction. 相似文献
17.
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
18.
Junes Ipaktschi Katja Reimann Michael Serafin Ansgar Dülmer 《Journal of organometallic chemistry》2003,670(1-2):66
Treatment of the η1-acetylide complex [(η5-C5H5)(CO)(NO)W---CC---C(CH3)3]Li (4) with 1,2-diiodoethane in THF at −78 °C, followed by the addition of Li---CC---R [R=C(CH3)3, C6H5, Si(CH3)3, 6a–6c] or n-C4H9Li and protonation with H2O, afforded the corresponding oxametallacyclopentadienyl complexes (η5-C5H5)W(I)(NO)[η2-O=C(CC---R)CH=CC(CH3)3] (7a–7c), 8c and (η5-C5H5)W(I)(NO)[η2-O=C(n-C4H9)CH=CC(CH3)3] (9). The formation of these metallafuran derivatives is rationalized by the electrophilic attack of 1,2-diiodoethane onto the metal center of 4 to form first the neutral complex [(η5-C5H5)(I)(CO)(NO)W---CC---C(CH3)3] (5). Subsequent nucleophilic addition of Li---CC---R 6a–6c or n-C4H9Li and a reductive elimination step followed by protonation leads to the products 7a–7c and 9. One reaction intermediate could be trapped with CF3SO3CH3 and characterized by a crystal structure analysis. The identity of another intermediate was established by infrared spectroscopic data. The oxametallacyclopentadienyl complex 10 forms in the presence of excess 1,2-diiodoethane through an alternative pathway and crystallizes as a clathrate containing iodine. 相似文献
19.
Sergey A. Anufriev Sergey V. Timofeev Alexei A. Anisimov Kyrill Yu. Suponitsky Igor B. Sivaev 《Molecules (Basel, Switzerland)》2020,25(23)
Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)2-3,3′-M(1,2-C2B9H10)2]− (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph3P)ClPd[8,8′- (MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} and {(COD)Rh[8,8′-(MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} were determined by single crystal X-ray diffraction. 相似文献
20.
The reactions of [Co(η-C5H5)(L)I2] with Na[S2CNR2] (R = alkyl or phenyl) give [Co(η-C5H5)(I)(S2CNR2)] (I) when L = CO and [Co(η-C5H5)(L)(S2CNR2)]I (II) when L is a tertiary phosphine, phosphite or stibine, or organo-isocyanide ligand. In similar reactions [Co(η-C5H5)(CO)(C3F7)I] gives [Co(η-C5H5)(C3F7)(S2CNMe2)] and [Mn(η-MeC5H4)(CO)2(NO)]PF6 forms [Mn(η-MeC5H4)(NO)(S2CNR2)]. The iodide ligands in I may be displaced by L, to give II, or by other ligands such as [CN]?, [NCS]?, H2O or pyridine whilst SnCl2 converts it to SnCl2I. The iodide counter-anion in II may be replaced by others to give [BPh4]?, [Co(CO)4]? or [NO3]? salts. However [CN]? acts differently and displaces (PhO)3P from [Co(η-C5H5){P(OPh)3}(S2CNMe)]I to give [Co(η-C5H5)(CN)(S2CNMe2)] which may be alkylated reversibly by MeI and irreversibly by MeSO3F to [Co(η-C5H5)(CNMe)(S2CNMe2)]+ salts. Conductivity measurements suggest that solutions of I in donor solvents are partially ionized with the formation of [Co(η-C5H5)(solvent)(S2CNR2)]+ I? species. The IR and 1H NMR spectra of the various complexes are reported. They are consistent with pseudo-octahedral “pianostool” molecular structures in which the bidentate dithiocarbamate ligands are coordinated to the metal atoms through both sulphur atoms. 相似文献