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201.
Saalfrank RW Deutscher C Maid H Ako AM Sperner S Nakajima T Bauer W Hampel F Hess BA van Eikema Hommes NJ Puchta R Heinemann FW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(8):1899-1905
In the reaction of the N-substituted diethanolamines (H(2)L(1-3)) (1-3) with calcium hydride followed by addition of iron(III) or indium(III) chloride, the iron wheels [Fe(6)Cl(6)(L(1))(6)] (4) and [Fe(6)Cl(6)(L(2))(6)] (6) or indium wheels [In(6)Cl(6)(L(1))(6)] (5), [In(6)Cl(6)(L(2))(6)] (8) and [In(6)Cl(6)(L(3))(6)] (9) were formed in excellent yields. Exchange of the chloride ions of 6 by thiocyanate ions afforded [Fe(6)(SCN)(6)(L(2))(6)] (7). Whereas the structures of 4, 5 and 7 were determined unequivocally by single-crystal X-ray analyses, complexes 8 and 9 were characterised by NMR spectroscopy. Contrary to what is normally presumed, the scaffolds of six-membered metallic wheels are not generally rigid, but rather undergo nondissociative topomerisation processes. This was shown by variable temperature (VT) (1)H NMR spectroscopy for the indium wheel [In(6)Cl(6)(L(1))(6)] (5) and is highlighted for the enantiotopomerisation of one indium centre [ 1/6[S(6)-5]<==>[1/6[S(6)-5']]. The self-assembly of metallic wheels, starting from diethanolamine dendrons, is an efficient strategy for the convergent synthesis of metallodendrimers. 相似文献
202.
Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids. 相似文献
203.
Ansgar Schäfer Christian Huber Jürgen Gauss Reinhart Ahlrichs 《Theoretical chemistry accounts》1993,87(1-2):29-40
Summary Experimentally known copper selenium clusters show extraordinary geometrical features, especially short Cu-Cu distances. We report the first theoretical investigation of Cu2Se and Cu4Se2. Various quantum chemical methods (SCF, MP2, CPF, CCSD, CCSD(T), LDF) are applied to determine the importance of dynamic electron correlation. We find that inclusion of correlation does not essentially change the electronic structure of the clusters but has a strong influence on geometries. To reduce the computational effort we apply effective core potentials (ECPs) in combination with small, but carefully optimized basis sets. The applicability of simple modellings of correlation energies for approximate inclusion of correlation effects in SCF geometry optimizations is tested. 相似文献
204.
Klampfl CW 《Journal of chromatography. A》2004,1044(1-2):131-144
This review discusses the development of capillary electrochromatography (CEC) coupled to mass spectrometric (MS) detection over the last few years. Major topics addressed are instrumental setups employed and applications of this technology published in the recent literature. The instrumental section includes a discussion of the most commonly used interfaces for the hyphenation of CEC and MS as well as ionization techniques. Applications reviewed in this paper come from a variety of different fields such as the analysis of biomolecules like proteins, peptides, amino acids or carbohydrates, chiral separations or the analysis of pharmaceutical an their metabolites in a series of matrices. 相似文献
205.
Adlhart C Sekiguchi O Uggerud E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):152-159
OH(+) is an extraordinarily strong oxidant. Complexed forms (L--OH(+)), such as H(2)OOH(+), H(3)NOH(+), or iron-porphyrin-OH(+) are the anticipated oxidants in many chemical reactions. While these molecules are typically not stable in solution, their isolation can be achieved in the gas phase. We report a systematic survey of the influence on L on the reactivity of L--OH(+) towards alkanes and halogenated alkanes, showing the tremendous influence of L on the reactivity of L--OH(+). With the help of with quantum chemical calculations, detailed mechanistic insights on these very general reactions are gained. The gas-phase pseudo-first-order reaction rates of H(2)OOH(+), H(3)NOH(+), and protonated 4-picoline-N-oxide towards isobutane and different halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2) have been determined by means of Fourier transform ion cyclotron resonance measurements. Reaction rates for H(2)OOH(+) are generally fast (7.2x10(-10)-3.0x10(-9) cm(3) mol(-1) s(-1)) and only in the cases HCF(3) and CF(4) no reactivity is observed. In contrast to this H(3)NOH(+) only reacts with tC(4)H(9)Cl (k(obs)=9.2x10(-10)), while 4-CH(3)-C(5)H(4)N-OH(+) is completely unreactive. While H(2)OOH(+) oxidizes alkanes by an initial hydride abstraction upon formation of a carbocation, it reacts with halogenated alkanes at the chlorine atom. Two mechanistic scenarios, namely oxidation at the halogen atom or proton transfer are found. Accurate proton affinities for HOOH, NH(2)OH, a series of alkanes C(n)H(2n+2) (n=1-4), and halogenated alkanes C(n)H(2n+1)Cl (n=1-4), HCF(3), CF(4), and CF(2)Cl(2), were calculated by using the G3 method and are in excellent agreement with experimental values, where available. The G3 enthalpies of reaction are also consistent with the observed products. The tendency for oxidation of alkanes by hydride abstraction is expressed in terms of G3 hydride affinities of the corresponding cationic products C(n)H(2n+1) (+) (n=1-4) and C(n)H(2n)Cl(+) (n=1-4). The hypersurface for the reaction of H(2)OOH(+) with CH(3)Cl and C(2)H(5)Cl was calculated at the B3 LYP, MP2, and G3(m*) level, underlining the three mechanistic scenarios in which the reaction is either induced by oxidation at the hydrogen or the halogen atom, or by proton transfer. 相似文献
206.
Christian Margot DanaP. Simmons Daniel Reichlin David Skuy 《Helvetica chimica acta》2004,87(10):2662-2684
Only one out of the four possible trans isomers of the important perfumery alcohol Norlimbanol® ( 1 ) possesses a very strong amber‐woody smell, the isomer 1A with (1′R,3S,6′S) absolute configuration. Its enantiomer 1B is almost odorless and devoid of amber‐woody character, whereas the diastereoisomers 1C and 1D are considerably weaker and perceptible only by the most‐sensitive persons. The same is true for a whole series of perceptual analogs of 1 , including β‐alkoxy alcohols. These ethers belong to two structural classes: [(2,2,6‐trimethylcyclohexyl)oxy]‐ (see 3, 4 , and 16 ) or {[2‐(tert‐butyl)cyclohexyl]oxy}alkan‐2‐ol derivatives (see 19 and 20 ; Table). A superimposition model allowing for good overlap of the respective hydroxylated side chains offers a tentative explanation for the shared perceptual characteristics of the two classes (Fig. 5). The lipophilic cyclohexane moieties present only a minimal overlap in this model, suggesting that quite larger molecules might possess the same smell. (S)‐Configured β‐alkoxy alcohols can conveniently be obtained on a larger scale by enantioselective reduction of the corresponding ketones (Scheme 9). 相似文献
207.
208.
Menadione (vitamin K3) undergoes a reversible two-electron transfer involving the quinone structure in acidic medium. As demonstrated by using cyclic voltammetry, the reduced form is more strongly adsorbed than the oxidized one. Stripping voltammetry of an adsorbed layer has been applied to the determination of this molecule after preconcentration of the reduced compound and scanning the potential towards less negative values. Adsorption, which is highly effective when stirring is used, approaches an equilibrium process in quiescent solution, as evidenced by a loss of part of the adsorbed material when stirring is stopped. A square-wave mode has been selected owing to its high sensitivity (the current is 20 times that for the differential pulse mode), but also to its high scan-rate, which minimizes the slow desorption process occurring during the scan. A concentration range from 2 × 10−10 to 5 × 10−7 M is easily investigated, the detection limit being 1.3 × 10−10 M. The influence of several operational parameters has also been considered. 相似文献
209.
210.
The rate coefficients for the dehydrogenation of ethane, propane, and isobutane with cationic rhodium atoms Rh+ and clusters Rh+ n of up to 30 atoms were measured under single-collision conditions in a Fourier-transform ion cyclotron resonance mass spectrometer. The reaction rates are cluster size dependent and parallel for all the three alkanes. While the reactions proceed close to the theoretical collision rates for a large number of clusters, characteristic minima are observed for Rh+ (5/6/9/19/28). The degree of dehydrogenation varies with the cluster size with maxima for 10< or =n< or =15 for the three alkanes and for n=3 and 2-4 in the cases of ethane and propane, respectively. However, complete dehydrogenation is only observed for the reaction of Rh+ 11 with propane. Dehydrogenation is remarkably selective and no other neutral products than H2 are observed. The results are interpreted in terms of likely cluster geometries. 相似文献