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991.
Cuesta L Huertos MA Morales D Pérez J Riera L Riera V Miguel D Menéndez-Velazquez A García-Granda S 《Inorganic chemistry》2007,46(7):2836-2845
Complexes [Re(ONCMe2)(CO)3(bipy)] (1) and [Re(ONCMe2)(CO)3(phen)] (2), synthesized by reaction of the respective triflato precursors [Re(OTf)(CO)3(N-N)] (N-N = bipy, phen) with KONCMe2, feature O-bonded monodentate oximato ligands. Compound [Re(CO)3(phen)(HONCMe2)]BAr'4 (3), with a monodentate N-bonded oxime ligand, was prepared by reaction of [Re(OTf)(CO)3(phen)], HONCMe2, and NaBAr'4. Deprotonation of 3 afforded 2. The oximato complexes reacted with p-tolylisocyanate, p-tolylisothiocyanate, maleic anhydride, and tetracyanoethylene, affording the products of the insertion of the electrophile into the Re-O bond, compounds 4-7. One representative of each type of compound was fully characterized, including single-crystal X-ray diffraction. The reactions of 1 and 2 with dimethylacetylenedicarboxylate were found to involve first an insertion as the ones mentioned above but followed by incorporation of water, loss of acetone, and formation of the charge-separated neutral amido complexes 9 and 10. The structure of 9 and 10 was determined by X-ray diffraction, and key features of their electronic distribution were studied using a topological analysis of the electron density as obtained from the Fourier map. 相似文献
992.
Dixon MC Daniel TA Hieda M Smilgies DM Chan MH Allara DL 《Langmuir : the ACS journal of surfaces and colloids》2007,23(5):2414-2422
Thin nanoporous gold (np-Au) films, ranging in thickness from approximately 40 to 1600 nm, have been prepared by selective chemical etching of Ag from Ag/Au alloy films supported on planar substrates. A combination of scanning electron microscopy (SEM) imaging, synchrotron grazing incidence small angle X-ray scattering, and N2 adsorption surface area measurements shows the films to exhibit a porous structure with intertwined gold fibrils exhibiting a spectrum of feature sizes and spacings ranging from several to hundreds of nanometers. Spectroscopic ellipsometry measurements (300-800 nm) reveal the onset of surface plasmon types of features with increase of film thicknesses into the approximately 200 nm film thickness range. Raman scattering measurements for films functionalized with a self-assembled monolayer formed from 4-fluorobenzenethiol show significant enhancements which vary sharply with film thickness and etching times. The maximum enhancement factors reach approximately 10(4) for 632.8 nm excitation, peak sharply in the approximately 200 nm thickness range for films prepared at optimum etching times, and show high spot to spot reproducibility with approximately 1 microm laser spot sizes, an indication that these films could be useful as durable, highly reproducible surface-enhanced Raman substrates. 相似文献
993.
Ronson TK Adams H Harding LP Pope SJ Sykes D Faulkner S Ward MD 《Dalton transactions (Cambridge, England : 2003)》2007,(10):1006-1022
A set of three potentially bridging ligands containing two tridentate chelating N,N',O-donor (pyrazole-pyridine-amide) donors separated by an o, m, or p-phenylene spacer has been prepared and their coordination chemistry with lanthanide(III) ions investigated. Ligand L(1) (p-phenylene spacer) forms complexes with a 2:3 M:L ratio according to the proportions used in the reaction mixture; the Ln(2)(L(1))(3) complexes contain two 9-coordinate Ln(III) centres with all three bridging ligands spanning both metal ions, and have a cylindrical (non-helical) 'mesocate' architecture. The 1:1 complexes display a range of structural types depending on the conditions used, including a cyclic Ln(4)(L(1))(4) tetranuclear helicate, a Ln(2)(L(1))(2) dinuclear mesocate, and an infinite one-dimensional coordination polymer in which metal ions and bridging ligands alternate along the sequence. ESMS studies indicate that the 1:1 complexes form a mixture of oligonuclear species {Ln(L(1))}(n) in solution (n up to 5) which are likely to be cyclic helicates. In contrast, ligands L(2) and L(3) (with o- and m-phenylene spacers, respectively) generally form dinuclear Ln(2)L(2) Ln(III) complexes in which the two ligands may be arranged in a helical or non-helical architecture about the two metal ions. These complexes also contain an additional exogenous bidentate bridging ligand, either acetate or formate, which has arisen from hydrolysis of solvent molecules promoted by the Lewis-acidity of the Ln(III) ions. Luminescence studies on some of the Nd(III) complexes showed that excitation into ligand-centred pi-pi* transitions result in the characteristic near-infrared luminescence from Nd(III) at 1060 nm. 相似文献
994.
Sametband M Shweky I Banin U Mandler D Almog J 《Chemical communications (Cambridge, England)》2007,(11):1142-1144
Two different types of nanoparticles dissolved in organic solution, gold stabilized by n-alkanethiols and CdSe/ZnS stabilized by n-alkane-amine, adhere preferentially to the ridges of latent fingerprints; the gold deposits catalyze silver electroless deposition from "Silver Physical Developer" (Ag-PD), an aqueous solution containing silver colloids stabilized by cationic surfactants, to form dark impressions of the ridge details; the hydrophobic capped gold nanoparticles significantly improve the intensity and clarity of the developed prints compared with Ag-PD alone; finger marks treated with CdSe/ZnS nanoparticles can be viewed directly, due to their fluorescence under UV illumination. 相似文献
995.
cis- and trans-3,4-Dichlorocyclobutene (I) react with Ni(CO)4 and AlCl3 to give (C4H4)NiCl2 · AlCl3 (II), while the bromo- and iodo-substituted cyclobutenes (III) without AlCl3 yield the complexes (C4H4)NiX2 (IVa, X Br; IVb, X I). Properties of II and IV are discussed and the presence of a C4H4 ring attached to nickel is likely from the results obtained. 相似文献
996.
An approximate analytic expression is derived, based on a novel model for the reactive–diffusive processes in a electrochemiluminescence (ecl) experiment. The physical system treated is one in which ecl is produced by stepping the voltage of a planar electrode to the diffusion-limited reduction value for an emitter species in the presence of a bulk oxidant precursor (9,10-DPA with benzoyl peroxide). The unknown rate constants are determined by a least-squares curve-fitting computer code. The model, though crude, provides an excellent fit to the ecl intensity versus time data, including the rise portion of the curve. 相似文献
997.
J. N. Spencer Eric S. Holmboe Daniel W. Firth Mindy R. Kirshenbaum 《Journal of solution chemistry》1981,10(10):745-756
Enthalpies of solution have been used to calculate transfer enthalpies for phenol, pyridine, and DMSO between the solvent cyclohexane and the solvents CCl4, benzene, and CHCl3. By use of model compounds, enthalpies due to interactions with phenol, pyridine, and DMSO have been determined. These enthalpies are used to calculate the effect of solvation relative to cyclohexane on hydrogen bonded complexes in CCl4 and benzene solvents. Correlations with enthalpies due to interactions and frequency shifts for the hydroxyl stretch in these solvents have also been made. 相似文献
998.
Daniel R. Coulter Ranty H. Liang Salvador Di Stefano Jovan Moacanin Amitava Gupta 《Chemical physics letters》1982,87(6):594-598
Transient emission studies following pulse radiolysis of solid poly(1-vinyl naphthalene) show existence of excited monomers and two excimers. Quenching experiments indicate that excimers are not formed directly by recombination of ions but probably by trapping of migrating monomeric excitation in performed traps whose density is approximately one in 103. 相似文献
999.
Differences in the ion flotation properties of palladium(II) and platinum(IV) chloro complexes in aqueous solutions are used to achieve separations of these metals. The anionic chloro complex PtCl2-6 is floated selectively with cationic surfactants of the type, RNR'3Br, from solutions of PdCl2-4 and various concentrations of hydrochloric acid. The palladium(II) does not float from solutions of ? 3.0 M HCl and the platinum(IV) floated from these solutions can be recovered free of palladium. However, the separation is incomplete as much of the platinum(IV) is also unfloated from these solutions. Quantitative separations are obtained by conversion of the palladium(II) to the cationic ammine, Pd(NH3)42+ with aqueous ammonia prior to flotation. The anionic chloro complex of platinum(IV) is unaffected by the presence of ammonia and is floated quantitatively with the surfactant n-hexadecyltri-n-propylammonium bromide from 0.01 M ammonia solutions. 相似文献
1000.
Daniel Karlsson Jakob Dahlin Åsa Marand Gunnar Skarping Marianne Dalene 《Analytica chimica acta》2005,534(2):263-269
A method for the determination of isocyanates as di-n-butyl amine (DBA) derivatives using tandem mass spectrometry (MS/MS) and electrospray ionisation (ESI) is presented. Multiple-reaction monitoring (MRM) of the protonated molecular ions and corresponding deuterium-labelled d9-DBA derivatives resulted in selective quantifications with correlation coefficients >0.998 for the DBA derivatives of isocyanic acid (ICA), methyl isocyanate (MIC), ethyl isocyanate (EIC), propyl isocyanate (PIC), phenyl isocyanate (PhI), 1,6-hexamethylene diisocyanate (HDI), 2,4-, 2,6-toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), 4,4′-methylenediphenyl diisocyanate (MDI), 3-ring MDI, 4-ring MDI, HDI-isocyanurate, HDI-diisocyanurate, HDI-biuret and HDI-dibiuret. The instrumental precision for 10 repeated injections of a solution containing 0.1 μg ml−1 of the studied derivatives was <2%. Performing MRM of the product ion [DBA + H]+ (m/z = 130) from the protonated molecular ion resulted in the lowest detection limits, down to 10 amol (for TDI). Quantification of concentrations below 10−6 of the occupational exposure limit (OEL) for TDI during 10 min of air sampling was made possible. In an effort to control the formation of alkali adducts, addition of lithium acetate to the mobile phase and monitoring of lithium adducts was evaluated. Having lithium present in the mobile phase resulted in complete domination of [M + Li]+ adducts, but detection limits for the studied compounds were not improved. Different deuterium-labelled derivatives as internal standards were evaluated. (1) DBA derivatives of deuterium-labelled isocyanates (d4-HDI, d3-2,4-TDI, d3-2,6-TDI and d2-MDI), (2) d9-DBA derivatives of the corresponding isocyanates and (3) d18-DBA derivatives of the corresponding isocyanates. An increase in number of deuterium in the molecule of the internal standard resulted in an increase in instrumental precision and a decrease in correlation within calibration series. 相似文献