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11.
12.
Fourier-transform ion-cyclotron-resonance (FTICR) mass spectrometry has been used to uncover the mechanisms by which FeO+ dehydrates heptan-4-one ( 5a ) and nonan-5-one ( 6a ) in the gas phase. The study of isotopomeric ketones provides evidence that H2O loss is not due to a 1,1-elimination, thus ruling out the intermediacy of high-valent iron-carbene species. Rather, H2O is generated in a formal 1,2-elimination involving the ω/ω ? 1 positions of the alkyl chain (‘remote C? H bond activation’). In the consecutive alkene/H2O elimination, the olefins (ethylene from 5a and propene from 6a ) originate from the terminal part of one alkyl chain, and the H-atom is transferred to the FeO+ moiety in the course of this process, builds up together with an H-atom from the ω/ω-1 position of the other alkyl chain the H2O molecule. In either case, the O-atom of H2O is provided by the FeO+ species. 相似文献
13.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献
14.
Mathias Höfler Jürgen Scheuren Detlef Spilker 《Journal of organometallic chemistry》1975,102(2):205-211
The complexes CpFe(CO)2SiBr3, CpFe(CO)2SiI3, CpFe(CO)2SiBr2(OMe), and CpFe(CO)2SiI(NH-cyclo-C6H11)2 are prepared by the reaction of CpFe(CO)2SiR3 (R = OMe, NH-cyclo-C6H11) with HBr, HI and CH3I. Treating CpFe(CO)2SiCl3 with a large excess of NaN3, KOCN or KSCN yields the first tri-pseudohalogensilyl—transition-metal-complexes. The compounds are characterized by IR and mass spectra. A new method of preparation of the already known complex CpFe(CO)2SiH3 is described starting from CpFe(CO)2SiCl3 and LiAlH4. 相似文献
15.
16.
Fundamental understanding of aerosol formation and particle transport are important aspects of understanding and improving
laser-ablation ICP–MS. To obtain more information about particles entering the ICP, laser aerosols generated under different
ablation conditions were collected on membrane filters. The particles and agglomerates were then visualised using scanning
electron microscope (SEM) imaging. To determine variations between different sample matrices, opaque (USGS BCR-2G) and transparent
(NIST SRM 610) glass, CaF2, and brass (MBH B26) samples were ablated using two different laser wavelengths, 193 and 266 nm. This study showed that the
condensed nano-particles (∼10 nm in diameter) formed by laser ablation reach the ICP as micron-sized agglomerates; this is
apparent from filters which contain only a few well-separated particles and particle agglomerates. Ablation experiments on
different metals and non-metals show that the structure of the agglomerates is matrix-dependent. Laser aerosols generated
from silicates and metals form linear agglomerates whereas particle-agglomerates of ablated CaF2 have cotton-like structures. Amongst other conditions, this study shows that the absorption characteristics of the sample
and the laser wavelength determine the production of micron-sized spherical particles formed by liquid droplet ejection. 相似文献
17.
We present Electron-Spin-Resonance experiments in the frequency range 35–420 GHz in magnetic fields up to 14 T and with temperatures down to 1.5 K. The quasi-onedimensionalS=1 Spin Systems NENP and NINO exhibit similar resonance-modes, which can be associated with transitions between excited states atq= and excitations from the groundstate. Groundstateexcitation can be explained with regard to a transverse staggered field due to inequivalent Ni2+-sites along the chains. Several features are discussed like polarisation-and temperature dependence of line-intensity and the angular and temperature-dependence of resonance-field. 相似文献
18.
Let G: (0, ∞) → (0, ∞) be logarithmically concave on a neighbourhood of ∞ and suppose limx→∞ G(x + δ)/G(x) = 1 for some δ > 0. Then, the functional equation $$g(x+1)=G(x)\cdot g(x),\ \ \ x\in (0,\infty),$$ admits, up to a multiplicative constant, at most one solution g: (0, ∞) → (0, ∞), geometrically convex on a neighbourhood of ∞. Sufficient conditions on G are given, for which also such a unique geometrically convex solution of (D) exists. This result improves the classical theorems of Bohr-Mollerup type and gives a new characterization of the gamma function and the q-gamma function for q ∈ (0, 1). 相似文献
19.
Detlef Gronau 《Results in Mathematics》1993,23(1-2):49-54
Let IK be either IR or ? and D an open set of IK containing 0 and starlike with respect to 0 (i.e. an open interval containig 0 in the case IK = IR). If f: D » IK is a continuous function with fixed point 0, then under certain conditions stated below we can prove for the kn- th iterates of f the following asymptotic formula: 1 $$f^{(kn)}\bigg({x \over n}\bigg )=\sum_{i-1}^r{1\over (nk)^i}\ f_i(kx)+o \bigg({1\over n^r}\bigg),$$ for n » ∞, k, n and r beeing positive integers and x close enough to 0. The functions f i are continuous and uniquely determined by f. In particular (1) holds for any function holomorphic on a neighbourhood of zero, having a convergent power series expansion of the form $$f(z)=z+a_2z^2+\cdots=\sum_{j=1}^\infty\ a_jz^j,\ a_j\in {\cal C},a_1=1,$$ and for any integers k, r with r > 0. 相似文献
20.
Detlef Gabel Claudia Bauer Mohamed E. El-Zaria Afaf R. Genady Udo Drfler 《Journal of organometallic chemistry》2003,680(1-2):23-26
The preparation and properties of the R1R2NH---B8H11NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine. 相似文献