[reaction: see text] The macrocyclic 18-diazo-1,4,7,10,13,16-hexaoxacyclononadeca-17,19-dione (3-diazo-2,4-dioxo-19-crown-6, 1) readily forms complexes with potassium (2, stability constant in methanol is K(K+) = 229 +/- 25 M(-1)) and sodium ions (3, K(Na+) = 84.2 +/- 7.9 M(-1) in methanol). According to B3LYP/6-31G+(d,p) calculations and temperature-dependent 1H NMR spectroscopy, the predominant conformation of 1 has a Z,Z arrangement of the diazo and carbonyl groups. The X-ray crystal structure analysis showed that the potassium complex (2) has the same Z,Z arrangement, while the sodium analogue (2) exists in conformation with Z,E geometry of the diazodicarbonyl moiety. Direct 254 nm photolysis of diazo compounds 1-3 in methanol results in the formation of 3-methoxy-2,4-dioxo-19-crown-6 (5), the product of the insertion of corresponding alpha,alpha'-dicarbonylcarbene into the O-H bond of the solvent. The triplet-sensitized photolysis of diazomalonates 1-3 produces 2,4-dioxo-19-crown-6 (6), which is apparently formed via the triplet state of the intervening carbene. 相似文献
This contribution describes the synthesis of gold nanorod (Au NR)/single-wall carbon nanotube (SWCNT) heterojunctions assembled directly on Si/SiOx substrates. SWCNTs are attached to amine-functionalized Si/SiOx substrates, and Au monolayer-protected clusters (MPCs) are adsorbed to the surface of SWCNTs through hydrophobic interactions. Seed-mediated reduction of HAuCl4 with ascorbic acid in the presence of cetyltrimethylammonium bromide (CTAB) onto the Au MPCs leads to the growth of larger Au nanostructures directly on the SWCNTs. Au NRs account for 19% of the nanostructures, some of which are attached directly to the sidewall and some at the ends of the SWCNTs. Raman spectroscopic measurements of SWCNTs before and after growth of the Au nanostructures reveal that the presence of Au leads to an approximately 50-fold enhancement of the Raman scattering signal. Combining 1D nanostructures of different materials (Au and carbon in this example) is of fundamental interest and may find use in nanoelectronics, chemical sensing, electrochemical, and spectroscopy applications. 相似文献
The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure. 相似文献
As a part of our general interest in the UV-Vis spectroscopy of multidentate mixed-donor ligands, the (salicylideneethylenediamine)Cu(II) complex has been prepared and characterized by elemental analyses, solubility in common solvents, molar conductivities, and ultraviolet (UV), and visible (Vis) spectroscopy. The combined results of spectrophotometric measurements and EPR spectra, as well as known the X-ray structure for solids, were used to determine the structure of the investigated complex in solutions. The spectra of [Cu(salen)] (H2salen = salicylideneethylenediamine), were measured in various solvents at room temperature, resolved by Gaussian analysis, and angular overlap model (AOM) treated in C2v symmetry. Because of overparametrization problems, the bis(salicylaldehyde)Cu(II) complex has been characterized and AOM treated. The results of this have been used for AOM studies of [Cu(salen)]. The effect of the solvents upon the - and -bonding ligand abilities is discussed. 相似文献
A new approach to polymeric supports useful for the immobilization of aldehydes and ketones via hydrazone linkers is reported. The new strategy gives supports with better properties and is effective for the synthesis of all supports previously used for the alkylation of ketones anchored as hydrazones. In contrast to other approaches, the new strategy also provided a polymer with an economical C2 spacer linker. The supports were used for immobilization of ketones 3-pentanone, acetone, N-benzylpiperidone, and aldehydes hexanal and 3-phenylpropanal in the form of their hydrazones. The polymer-supported hydrazones were subjected to alpha-alkylation (LDA/RX) followed by acidic, reductive, or oxidative cleavage/workup procedures to provide alpha-alkylated aldehydes or ketones as well as corresponding primary amines, alcohols, nitriles or acids. 相似文献
Starting with (S)-1-benzylprolinamine and α-hydroxyimino ketones, enantiomerically pure bisheterocyclic imidazole N-oxides bearing the (S)-configured N-benzyl(pyrrolidin-2-yl)methyl residue were prepared. These N-oxides reacted with 2,2,4,4-tetramethylcyclobutane-1,3-dithione to give the corresponding optically active imidazole-2-thione derivatives via a sulfur transfer reaction. Reduction of the N-oxides with Raney-nickel led to deoxygenation, whereas catalytic hydrogenation (Pd/C) in ethanol occurred with simultaneous deoxygenation and debenzylation, leading to optically active 1-(pyrrolidin-2-yl)methyl-1H-imidazoles. Alkylation of the prepared imidazole N-oxides and their respective imidazoles with butyl and hexyl bromide and subsequent anion exchange gave optically active N-alkoxy- and N-alkylimidazolium tetrafluoroborates, respectively, with the properties of ‘room temperature ionic liquids’. 相似文献
A search for new drugs that overcome the multidrug resistance of microorganisms or are effective against cancer cells prompted us to investigate the binary and ternary Cu(II) complexes containing L-arginine, [CuCl(L-Arg)(phen)]Cl·2H2O (phen = 1,10-phenanthroline) ( 1 ) and [Cu(L-Arg)2(H2O)]C2O4·6H2O ( 2 ), for which crystal and molecular structures were characterized previously. In order to discuss the biological function, the complexes have been screened for their antitumor activity against A549 (human lung cancer cells), HepG2 (human liver hepatocellular carcinoma cells) and antimicrobial activity. To identify the complexes forms existing in the solutions of 1 and 2 crystals, the results obtained from EPR, NIR–Vis–UV and MS (mass spectrometry) measurements were correlated with those from analysis of potentiometric titration of Cu(II)―L-Arg and Cu(II)―L-Arg―phen systems. This comprehensive study indicated that the [Cu(L-Arg)(phen)]2+ and [Cu(L-Arg)2]2+ species are dominant in the solution. Complexes 1 and 2 were found to present specific ligand-dependent cytotoxic and antiproliferative potential against cancer cells. They also show antibacterial activity against Gram-positive and Gram-negative bacteria as well as display antifungal properties. 相似文献
Conformational propensities of N-t-butoxycarbonyl-glycine-(E/Z)-dehydrophenylalanine N′-methylamides (Boc-Gly-(E/Z)-ΔPhe-NHMe) in chloroform were investigated by NMR and IR techniques. The low-temperature crystal structure of the E isomer was determined by single crystal X-ray diffraction and the experimental data were elaborated by theoretical calculations using DFT (B3LYP, M06-2X) and MP2 approaches. The β-turn tendencies for both isomers were determined in the gas phase and in the presence of solvent. The obtained results reveal that the configuration of ΔPhe residue significantly affects the conformations of the studied dehydropeptides. The tendency to adopt β-turn conformations is significantly lower for the E isomer (Boc-Gly-(E)-ΔPhe-NHMe), both in gas phase and in chloroform solution.