1-(Organosulfonyloxy)-3(1H)-1,2-benziodoxoles: Preparation and Reactions with Alkynyltrimethylsilanes

Organosulfonyloxy derivatives of 1,2-benziodoxol-3(1H)-one (3a-c) and 3,3-bis(trifluoromethyl)-3(1H)-1,2-benziodoxole (5a-c) can be prepared in high yield by the reaction of 1-hydroxybenziodoxoles 1 or 4 and the corresponding sulfonic acids or Me(3)SiOTf in the form of stable, but moderately hygroscopic, microcrystalline solids. Reaction of the triflate derivatives 3a and 5a with alkynyltrimethylsilanes affords either alkynyliodonium triflates 6, or (E)-beta-(trifluoromethanesulfonyloxy)alkenyliodonium triflates 7, while the same reaction in the presence of pyridine selectively gives the respective 1-alkynylbenziodoxoles 8 and 9 in 82-90% yield.     

1-[Hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes: Stable, Fluoroalkyl Analogs of Koser's Reagent

1-[Hydroxy(sulfonyloxy)iodo]-1H,1H-perfluoroalkanes 3 [R(f)CH(2)I(OH)OSO(2)R; R = CH(3), CF(3), p-CH(3)C(6)H(4), R(f) = CF(3), C(2)F(5)] can be prepared in two steps from the appropriate iodofluoroalkanes by oxidation with peroxytrifluoroacetic acid and subsequent reaction with TsOH, MsOH, or Me(3)SiOTf. The tosylate derivative 3a reacts with silyl enol ethers under mild conditions to give the respective alpha-(tosyloxy) ketones. A similar reaction of cyclohexene furnishes cis-1,2-bis(tosyloxy)cyclohexane as the major product. Triflates 3c,f react with (trimethylsilyl)arenes under mild conditions to afford the respective (fluoroalkyl) (aryl)iodonium triflates 7, while the analogous reaction with alkynyltrimethylsilanes leads to novel (fluoroalkyl)(alkynyl)iodonium salts 8.     

Electrochemical and spectroscopic characterization of the novel charge-transfer ground state in diimine complexes of ytterbocene

The novel charge-transfer ground state found in alpha,alpha'-diimine adducts of ytterbocene (C(5)Me(5))(2)Yb(L) [L = 2,2'-bipyridine (bpy) and 1,10-phenanthroline (phen)] in which an electron is spontaneously transferred from the f(14) metal center into the lowest unoccupied (pi*) molecular orbital (LUMO) of the diimine ligand to give an f(13)-L(*)(-) ground-state electronic configuration has been characterized by cyclic voltammetry, UV-vis-near-IR electronic absorption, and resonance Raman spectroscopies. The voltammetric data demonstrate that the diimine ligand LUMO is stabilized and the metal f orbital is destabilized by approximately 1.0 V each upon complexation for both bpy and phen adducts. The separation between the ligand-based oxidation wave (L(0/-)) and the metal-based reduction wave (Yb(3+/2+)) in the ytterbocene adducts is 0.79 V for both bpy and phen complexes. The UV-vis-near-IR absorption spectroscopic data for both the neutral adducts and the one-electron-oxidized complexes are consistent with those reported recently, but previously unreported bands in the near-IR have been recorded and assigned to ligand (pi*)-to-metal (f orbital) charge-transfer (LMCT) transitions. These optical electronic excited states are the converse of the ground-state charge-transfer process (e.g., f(13)-L(*-) <--> f(14)-L(0)). These new bands occur at approximately 5000 cm(-1) in both adducts, consistent with predictions from electrochemical data, and the spacings of the resolved vibronic bands in these transitions are consistent with the removal of an electron from the ligand pi* orbital. The unusually large intensity observed in the f --> f intraconfiguration transitions for the neutral phenanthroline adduct is discussed in terms of an intensity-borrowing mechanism involving the low-energy LMCT states. Raman vibrational data clearly reveal resonance enhancement for excitation into the low-lying pi* --> pi* ligand-localized excited states, and comparison of the vibrational energies with those reported for alkali-metal-reduced diimine ligands confirms that the ligands in the adducts are reduced radical anions. Differences in the resonance enhancement pattern for the modes in the bipyridine adduct with excitation into different pi* --> pi* levels illustrate the different nodal structures that exist in the various low-lying pi* orbitals.     

PHELIX – Status and First Experiments

The high-energy high-power laser system PHELIX (Petawatt High Energy Laser for heavy Ion eXperiments) [1] is currently under construction at the Gesellschaft fuer Schwerionenforschung mbH (GSI) Darmstadt. With PHELIX GSI will offer the unique combination of a high-current, high-energy (GeV/u) heavy-ion beam with an intense laser beam. This will open the door to a variety of fundamental science issues in the field of atomic physics, plasma physics and nuclear physics. The project will gain further interest in the near future by the dramatic increase of the accelerator performance with the starting FAIR project at GSI [2]. This paper reports the current status of the project as well as the laser architecture. The proposed physics program and a first experiment carried out with PHELIX, the realization of a transient collisionally excited x-ray laser [3], will also be reviewed briefly.     

Zero-angle depolarized light scattering of a colloidal polymer

The potential of zero-angle depolarized scattering for measuring the size distributions of optically anisotropic particles is considered. To illustrate the method, an analysis of Fluon, a teflon latex suspension, is presented. Homodyne correlation functions having signal-to-noise characteristics every bit as good as conventional unpolarized finite-angle measurements enabled confident application of a smoothed exponential sampling algorithm to obtain the decay rate distribution, which was converted to a size distribution with certain approximations. The size distribution obtained from light scattering agrees well with that from electron microscopy.     

Transient collisionally excited X-ray laser in nickel-like zirconium pumped with the PHELIX laser facility

A transient collisionally excited X-ray laser has been put into operation using the front end of the PHELIX laser system as a pump laser. Strong lasing at 22 nm has been observed in nickel-like zirconium. PACS 42.60.-v; 42.55.Vc; 42.62.Fi     

Preparation and chemistry of stable azidoiodinanes: 1-Azido-3,3-bis(trifluoromethyl)-3-(1H)-1,2-benziodoxol and 1-Azido-1,2-benziodoxol-3-(1H)-one

Azidoiodinanes 2,4,6 can be prepared from benziodoxols 1,3 and trimethylsilyl azide in the form of stable, crystalline compounds. These compounds are potentially useful reagents for electrophilic azidonation of organic substrates. For example, reaction of azide 6 with cyclohexene affords 2-azidocyclohexanone 7 in moderate yield.