共查询到20条相似文献,搜索用时 31 毫秒
1.
Michler's ketone (MK) and tetracyanoethene (TCNE) may be used as a UV-vis probe to investigate the solvent properties of ionic liquids (ILs). In molecular solvents, MK and TCNE give an electron donor-acceptor (EDA) complex, a zwitterionic species or a radical ion pair, depending on the aprotic or protic nature of the solvent and on its ionizing power. In agreement with the behavior observed in aprotic solvents, only the EDA complex was detected in ILs bearing low donor anions (beta < 0.7). The formation constant determined in [bmim][Tf(2)N] (K(c) = 5.6 (0.5) M(-1)) is similar to that measured in 1,2-dichloroethane at 25 degrees C. The visible absorption maximum (nu(max,CTC)) of the EDA complex is quantitatively described by a multiple correlation using the Kamlet-Taft pi, beta, and alpha parameters of the solvents. The H-bond donating capacity of ILs is not sufficient to determine the transformation of the EDA complex into the zwitterionic species, but the Kamlet-Taft alpha parameter seems to affect the position of the absorption band. The high ionization power of ILs, moreover, favors the slow dissociation of the EDA complex into its corresponding radical ion pair; this behavior generally characterizes highly polar and highly ionizing protic solvents, such as TFE and HFI. Finally, since the formation of the EDA complex is strongly affected by the presence of impurities, traces of nucleophiles (chloride or amines) or water may be easily detected through the change of the solution color. 相似文献
2.
Hasani M Rezaei A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2006,65(5):1093-1097
The charge-transfer complex formation of iodine with antipyrine has been studied spectrophotometrically in chloroform, dichloromethane (DCM) and 1,2-dichloroethane (DCE) solutions at 25 degrees C. The results indicate the formation of 1:1 charge-transfer complexes. The observed time dependence of the charge-transfer band and subsequent formation of I(3)(-) in solution were related to the slow transformation of the initially formed 1:1 antipyrine:I(2) outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The values of the equilibrium constant, K, are calculated for each complex and the influence of the solvent properties on the formation of EDA complexes and the rates of subsequent reaction is evaluated. 相似文献
3.
Cellulose - Cellulose I crystals swell on exposure to ethylenediamine (EDA) molecules to form a cellulose I–EDA complex, and successive extraction of EDA molecules converts the complex... 相似文献
4.
The quaternary ammonium salts find extensive use in a variety of chemical applications as surfactants and phase-transfer catalysts. Even though the interaction of the surfactants with various systems has been studied rather extensively, very little information is available on how the phase-transfer catalysts (PTC) interact with the dipolar systems in nonpolar media and how/whether these solubilizing agents affect the properties of the dissolved molecules. In this paper, the interaction of several tetraalkylammonium salts, commonly used as PTC, with a number of electron donor-acceptor (EDA) systems has been studied by absorption and fluorescence spectroscopy. The phase-transfer catalysts have been found to affect both the absorption and fluorescence properties of the EDA systems. The spectral changes of the EDA molecules induced by the tetraalkylammonium salts suggest the formation of an 1:1 complex between the two in nonpolar media. An electrostatic interaction between the phase-transfer catalysts (which exist as ion pairs in nonpolar media) and the dipolar molecules is shown to be the driving force for the formation of the complex. The dependence of the formation constant of the complex on the polarity of the media suggests a charge-transfer nature of the complex. It is shown that the anionic component of the salts serves as a source of electron to the positive end of the dipolar molecule, while the tetraalkylammonium cation, besides helping solubilization of its anionic counterpart in the nonpolar media, serves neutralizing the negative charge at the acceptor end of the EDA molecule. In effect, a cooperative influence of the cationic and anionic components of the PTC enhances the charge separation within the dipolar fluorophores. On the basis of the PTC-induced changes in the photophysical behavior of the EDA molecules, a possible structure for the 1:1 complex has been proposed. It has been concluded that a phase-transfer catalyst should not be treated as an innocuous substance that merely helps transfer of a polar substance from a polar to a nonpolar environment. Instead, it is demonstrated that the association of a PTC with a dipolar species can significantly change various properties of the latter. 相似文献
5.
研究了1-4丁炔二醇和乙二胺作为添加剂对在离子液体1-甲基-3-甲基咪唑三氟甲磺酸盐中电沉积Cu的影响。紫外可见光吸收光谱结果表明,当采用1-4丁炔二醇作为添加剂时,1-4丁炔二醇吸附在工作电极表面且未与溶液中的Cu2+形成配合物。扫描电镜测试结果表明由于1-4丁炔二醇与离子液体的正离子的竞争吸附使得Cu的沉积电势发生正移并使镀层表面更加均匀平整。当采用乙二胺作为添加剂时,紫外可见光吸收光谱和循环伏安测试结果表明乙二胺与溶液中的Cu2+离子形成带有正电荷的络合离子使得Cu的沉积电势发生正移,扫描电镜和原子力显微镜测试结果表明得到了更加均匀的镀层。当同时加入1-4丁炔二醇和乙二胺时,Cu的沉积电势仍然发生正移并得到具有纳米粒径的镀层。 相似文献
6.
X‐Ray Characterization of an Electron Donor–Acceptor Complex that Drives the Photochemical Alkylation of Indoles
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sandeep R. Kandukuri Ana Bahamonde Dr. Indranil Chatterjee Dr. Igor D. Jurberg Eduardo C. Escudero‐Adán Prof. Dr. Paolo Melchiorre 《Angewandte Chemie (International ed. in English)》2015,54(5):1485-1489
A metal‐free, photochemical strategy for the direct alkylation of indoles was developed. The reaction, which occurs at ambient temperature, is driven by the photochemical activity of electron donor–acceptor (EDA) complexes, generated upon association of substituted 1H‐indoles with electron‐accepting benzyl and phenacyl bromides. Significant mechanistic insights are provided by the X‐ray single‐crystal analysis of an EDA complex relevant to the photoalkylation and the determination of the quantum yield (Φ) of the process. 相似文献
7.
Hasani M Akbari S 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(1):139-144
Interaction of 2-aminomethyl-15-crown-5 (AM15C5) with iodine has been investigated spectrophotometrically in chloroform and 1,2-dichloroethane (1,2-DCE) solutions. The observed time dependence of the charge-transfer band and subsequent formation of I(3)(-) in solution were related to the slow transformation of the initially formed 1:1 AM15C5.I(2) outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion. The pseudo-first-order rate constants were evaluated from the absorbance- and conductivity-time data. The stoichiometry and formation constants of the resulting EDA complexes have also been determined. Thermodynamic parameters, Delta H degrees and Delta S degrees , of the complexes have been determined from the temperature dependence of stability constants by Van't Hoff equation. The results indicate that iodine complexes of AM15C5 in both solvents are enthalpy stabilized but entropy destabilized. The influence of solvent properties on the kinetics and stability of the resulting charge-transfer complexes are discussed. 相似文献
8.
Sumanta Bhattacharya Shrabanti Bhattacharya Banerjee Kalyan Ghosh Sukalyan Basu Manas Banerjee 《Journal of solution chemistry》2006,35(4):519-539
Electron donor–acceptor (EDA) complex formation of o-chloranil with six different phosphine oxides and tri-n-butyl phosphate (TBP) has been studied in CCl 4 solution by the UV-VIS absorption spectrophotometric technique. An absorption band due to a charge–transfer (CT) transition is observed in the visible region. Utilizing the CT transition energy, the electron affinity of o-chloranil in solution has been calculated. Degrees of charge transfer, and oscillator and transition dipole strengths have also been calculated for all of the investigated EDA complexes. Except for TBP, other phosphine oxides, viz., tri-n-octyl phosphine oxide, tri-n-butyl phosphine oxide, triphenyl phosphine, octyl(phenyl)-N,N-diisobutylcarbamoylphosphine oxide, octyl(phenyl)-N,N-dicyclohexylcarbamoylmethylphosphine oxide and octyl(phenyl)-N,N-diisopropylcarbamoylmethylphosphine oxide have been shown to form stable 1:1 EDA complexes with o-chloranil. The complex of TBP with o-chloranil decays slowly into a secondary product. Formation constants of the EDA complexes have been determined. 相似文献
9.
研究了1-4丁炔二醇和乙二胺作为添加剂对在离子液体1-甲基-3-甲基咪唑三氟甲磺酸盐中电沉积Cu的影响。紫外可见光吸收光谱结果表明,当采用1-4丁炔二醇作为添加剂时,1-4丁炔二醇吸附在工作电极表面且未与溶液中的Cu2+形成配合物。扫描电镜测试结果表明由于1-4丁炔二醇与离子液体的正离子的竞争吸附使得Cu的沉积电势发生正移并使镀层表面更加均匀平整。当采用乙二胺作为添加剂时,紫外可见光吸收光谱和循环伏安测试结果表明乙二胺与溶液中的Cu2+离子形成带有正电荷的络合离子使得Cu的沉积电势发生正移,扫描电镜和原子力显微镜测试结果表明得到了更加均匀的镀层。当同时加入1-4丁炔二醇和乙二胺时,Cu的沉积电势仍然发生正移并得到具有纳米粒径的镀层。 相似文献
10.
Neelgund GM Magadum SR Budni ML 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):480-487
The electron donor–acceptor (EDA) interaction between 2,3-dicyano-1,4-naphthoquinone (DCNQ) and 3,4-dimethylaniline (3,4-DMA) is studied in chloroform, dichloromethane and 1:1 (v/v) mixture of chloroform and dichloromethane. The rate of formation of the product was measured as a function of time using UV–vis spectrophotometer. The formation constant (K) and molar extinction coefficient (?) values for the formation of EDA complex were evaluated in the temperature range of 20–35 °C. The pseudo-first-order rate constant (k1) and the second-order rate constant (k2) for the disappearance of EDA complex and for the formation of product were evaluated. The activation parameters (ΔH#, ΔS# and ΔG#) of the reaction were determined by temperature dependence of rate constants using the Arrhenius plots. The effect of relative permittivity of the medium on the reaction is discussed. The observed results indicate that formation of final product proceeds through initial formation of EDA complex as an intermediate. The product of the reaction was purified by column chromatography method and identified as 3-(N-3,4-dimethyl-phenylamino)-2-cyano-1,4-naphthoquinone by elemental analysis, IR and NMR spectroscopy. On the basis of kinetic, analytical and spectroscopic results, a plausible mechanism for the formation of EDA complex and its transformation into product is proposed. 相似文献
11.
Yuanzheng Cheng Xiangai Yuan Prof. Dr. Jing Ma Prof. Dr. Shouyun Yu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(23):8355-8359
A novel electron‐donor–acceptor (EDA) complex‐mediated direct C?H trifluoromethylation of arenes with Umemoto’s reagent has been developed. This transformation has been enabled by an unprecedented EDA complex formed by Umemoto’s reagent and an amine, which was supported by experiments and theoretical calculations. The radical‐based methodology presented here allows to access highly‐functionalized trifluoromethyl arenes in up to 81 % chemical yield. 相似文献
12.
A Combined Theoretical Calculation and Hirshfeld Surface Analysis of Cooperative Non‐covalent Interactions in the Crystal Packing in [Cu(L1)2(EDA)]
下载免费PDF全文
![点击此处可从《无机化学与普通化学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The monomeric complex [Cu(L1)2(EDA)] ( I ) [L1 = 2,4‐dinitrobenzoic acid, EDA = ethylenediamine), was solved in orthorhombic space group (Pbca) and characterized by elemental analysis, IR spectroscopy, powder XRD analysis, and single‐crystal X‐ray crystallography, in addition to photoluminescence and thermal stability investigation. The Cu2+ ion is connecting with two L1 through monodentate mode of coordination and two nitrogen atoms from EDA. I is associated through cooperative non‐covalent interactions, which are also responsible for the strengthening of the molecular assembly and organize it into a supramolecular 2D motif. Hirshfeld surface analysis was also applied to investigate the cooperative non‐covalent supramolecular interactions and the results were compared with the single‐crystal X‐ray diffraction data. To get clear insights into the both species, electronic properties such as HOMO‐LUMO, electronic chemical potential and other derived parameters were also highlighted using DFT calculations at M06‐2X/ 6‐31G** level of theory. The observed photoluminescence of complex I arises mainly from an excited LLCT state with small MLCT contributions (from Cu2+ to the unoccupied p orbital of L1). The presented work exhibits another example of the utility and prosperity of such kinds of subtle information and features especially, and for complex I at molecular level, generally. 相似文献
13.
Biermann U Butte W Koch R Fokou PA Türünç O Meier MA Metzger JO 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(26):8201-8207
A kinetic study of the dodecanethiol-catalyzed cis/trans isomerization of methyl oleate (cis-2) without added initiator was performed by focusing on the initiation of the radical chain reaction. The reaction orders of the rate of isomerization were 2 and 0.5 for 1 and cis-2, respectively, and an overall kinetic isotope effect k(H)/k(D) of 2.8 was found. The initiation was shown to be a complex reaction. The electron-donor/-acceptor (EDA) complex of dodecanethiol (1) and cis-2 formed in a pre-equilibrium reacts with thiol 1 to give a stearyl and a sulfuranyl radical through molecule-assisted homolysis (MAH) of the sulfur-hydrogen bond. Fragmentation of the latter gives the thiyl radical, which catalyzes the cis/trans isomerization. A computational study of the EDA complex, MAH reaction, and the sulfuranyl radical calculated that the activation energy of the isomerization was in good agreement with the experimental result of E(A)=82?kJ M(-1). Overall, the results may explain that the thermal generation of thiyl radicals without any initiator is responsible for many well-known thermally initiated addition reactions of thiol compounds to alkenes and their respective polymerizations and for the low shelf-life stability of cis-unsaturated thiol compounds and of mixtures of alkenes and thiol compounds. 相似文献
14.
Caballero A Díaz-Requejo MM Belderraín TR Nicasio MC Trofimenko S Pérez PJ 《Journal of the American Chemical Society》2003,125(6):1446-1447
The complex Tp(Br3)Cu(NCMe) (1) is an excellent catalyst for the regioselective carbene transfer reaction to tertiary C-H bonds of hydrocarbons, at room temperature, using the readily available ethyl diazoacetate (EDA) as the carbene source. 相似文献
15.
A solution of 1,2,4,5-tetracyanobenzene (TCNB) in 2-methyltetrahehydrofuran (MTHF), in which a solute—solvent electron donor—acceptor (EDA) complex is formed, has been photoirradiated by 350–400 nm light at 77 K so as to excite only benzophenone. The intensity dependence of the exciting UV light on the photoinduced radical-anion formation of TCNB has been studied by means of optical absorption, suggesting a sensitized biphotonic ionic dissociation of the EDA complex. 相似文献
16.
The reaction between Cr(CO)5[C6H6] and ethyl diazoacetate (EDA) has been studied using the technique of laser flash photolysis. Results indicate that the Cr(CO)5 fragment reacts very rapidly with the EDA ligand. Low temperature spectroscopic studies suggest that in the case of W(CO)5, and by analogy also in the case of Cr(CO)5, the initial adduct between the pentacarbonyl fragment and EDA is one where the oxygen atom of the diazocarbonyl ligand is bound to the metal center. This kinetic product is then converted to a thermodynamically favored complex which is tentatively assigned as the nitrogen bound W(CO)5-EDA complex that appears to be stable at r.t. 相似文献
17.
Liang JG Zhang SS Ai XP Ji XH He ZK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2974-2978
The interaction of some diamines (ethylenediamine (EDA), 1,6-hexanediamine (HDA), o-phenylenediamine (OPD)) with CdSe quantum dots (QDs) is reported. With increasing concentration of EDA from 0 to 2.0 x 10(-6) mol l(-1), slight fluorescence enhancement is observed. However, the CdSe QDs fluorescence quenching is seen at relatively higher concentration of EDA. There is a red-shift of 0-7 nm in fluorescence emission spectra of CdSe QDs when the concentration of EDA is changed from 2.0 x 10(-6) to 8.0 x 10(-6) mol l(-1). The resonance light scattering (RLS) spectra of CdSe QDs have little change when the concentration of EDA is less than 5.0 x 10(-6) mol l(-1). It indicates there are little large particles formed in the solution. However, a significant increase of the RLS is observed in the 300-500 nm wavelength range after adding higher concentration than 5.0 x 10(-6) mol l(-1) EDA, which could be attributed to the large particles formed. The interaction between HDA and CdSe QDs is similar to that of EDA. However, with the OPD, it is found that the interaction is much different from those of EDA, HDA, and that the quenching, even at low concentration, is effective for CdSe QDs emission. The quenching phenomenon could be explained by a surface bound complexation equilibrium model. 相似文献
18.
Jean-Paul Silvestre Nguyen Quy Dao et Pascale Salvini 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):771-779
The organic complex salt [H 3 N--CH 2 --CH 2 --NH 3 ][C(CH 3 )(OH)(PO 3 H 2 )(PO 3 H)] 2 is obtained by reaction between the hydroxyethylidenebisphosphonic acid (HEBP) and the ethylenediamine (EDA) in aqueous medium. This compound, the first where the cation is an organic base, crystallizes with the monoclinic space group P2 1 / c (n°;14) and a = 6.867(1) Å, b = 11.665(2) Å, c = 10.977(2) Å, g = 101.85(4)°;, V = 861.2(2) Å 3 , Z = 2. The cohesion of the crystal structure is assumed exclusively by a dense network of hydrogen bonds between two HEDP m and between one HEDP m and one EDA 2+ . 相似文献
19.
半夹芯式碳硼烷16e金属有机化合物CpCo(S2C2B10H10)与重氮乙酸乙酯及联烯在室温下反应,生成化合物1和2。在化合物1和2中,一分子重氮乙酸乙酯与一分子联烯以头-头方式插入Co-B键之间使碳硼烷B(3)/(6)位发生B-H键活化生成B-C键,另有一分子重氮乙酸乙酯使Co-S断裂形成硫叶立德。分别采用红外、核磁、元素分析、质谱和单晶X射线衍射等表征方法对化合物1和2进行了结构表征。 相似文献
20.
Stepień M Donnio B Sessler JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(24):6853-6863
A number of substituted zinc(II) porphycenes and porphyrins have been synthesized as potentially mesogenic materials. One of the resulting porphycenes, bearing eight decyloxy chains, exhibits two mesophases, a transient lamellar phase (Lam) and a highly ordered lamello-columnar phase (L(Col)), with remarkably different structural characteristics. The same zinc(II) porphycene also forms an electron donor-acceptor (EDA) complex with tetracyanoquinodimethane (TCNQ), generating a hexagonal columnar mesophase (Col(h)) that is thermally stable up to ca. 200 degrees C. The EDA interaction between porphycene and TCNQ has been probed using electronic and vibrational spectroscopy. A mixture of zinc(II) porphyrins, isomeric with the above porphycene complex, forms a rectangular columnar mesophase (Col(r)). 相似文献