Two-photon laser spectroscopy of the muonium 1S–2S transition

The 1² S _1/2(F=1)?2² S _1/2(F=1) energy interval in muonium has been investigated by Doppler-free two-photon laser spectroscopy. The transition was observed by uniquely identifying and counting the muons released after the photoionization of the 2S state by the same laser field. The measured transition frequency of 2455 528016(58)(43) MHz is in good agreement with QED calculations. The experiment can be interpreted as a test of the Lamb shift contributions at the 1% level. The method is also well suited for a precise determination of the mass of the positive muon in a muoniumhydrogen isotope shift measurement.     

Massenspektrometrische Untersuchung aromatischer Halogenide der Summenformel C9H11Cl: Mechanismus der Äthylen-Abspaltung aus dem Ion [M ? Cl]+˙

By investigation of isomeric ²H- and ¹³C-labelled C₉H₁₁ Cl-compounds it has been shown that the ion [M ? Cl]⁺ is transformed mainly to the ion [C₇H₇]⁺ via C₂H₄-elimination from alkyl-substituted tropylium-ions. Phenyl-cyclopropane-cations play only a small part, if at all, in this fragmentation process.     

Radical cyclization cascade involving ynamides: an original access to nitrogen-containing heterocycles

A radical cascade involving a 5-exo-dig cyclization followed by a 6-endo-trig radical trapping transforms ynamides into heterogeneous polycyclic compounds in good yields. This leads interestingly to the formation of isoindols, isoindolinones, and pyridoisoindolones. [reaction: see text]     

The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

Monolayers as models for supported catalysts: zirconium phosphonate films containing manganese(III) porphyrins

Organized monolayer films of a manganese tetraphenylporphyrin have been prepared and used as supported oxidation catalysts. Manganese 5,10,15,20-tetrakis(tetrafluorophenyl-4'-octadecyloxyphosphonic acid) porphyrin (1) has been immobilized as a monolayer film by a combination of Langmuir-Blodgett (LB) and self-assembled monolayer techniques that use zirconium phosphonate linkages to bind the molecule to the surface. Analysis by FTIR, XPS, UV-vis and polarized optical spectroscopy show that the films consist of noninteracting molecules effectively anchored and oriented nearly parallel to the surface. The monolayer films are stable to the solvent and temperature conditions needed to explore organic oxidations. The activity of films of 1 toward the epoxidation of cyclooctene using iodosylbenzene as the oxidant was compared to that of Manganese 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin (2) and 1 under equivalent homogeneous conditions. The immobilized porphyrin 1 shows an enhanced activity relative to either homogeneous reaction. The main difference between 1 and 2 is the four alkyl phosphonate arms in 1 designed to incorporate the porphyrin within the films. The increased activity of immobilized 1 is a combination of the porphyrin structure, which prohibits the formation of mu-oxo dimers even in solution, and a change in conformation when anchored to the surface. The study demonstrates that careful monolayer studies can provide useful models for the design and study of supported molecular catalyst systems.