Mass separator for radioactive isotopes

A new isotope separator has been designed, constructed, and put into routine operation for separation of ¹³³Xe providing a major advancement and significant cost reduction in preparation of this radioactive isotope. The design features and advantages are discussed that expedite high purity separation of relatively small quantities of this isotope. These advantages could be easily used to expedite separation of other shorter-lived radioactive isotopes.     

Solvent Effect and Reactivity Trend in the Aerobic Oxidation of 1,3‐Propanediols over Gold Supported on Titania: NMR Diffusion and Relaxation Studies

In recent work, it was reported that changes in solvent composition, precisely the addition of water, significantly inhibits the catalytic activity of Au/TiO₂ catalyst in the aerobic oxidation of 1,4‐butanediol in methanol due to changes in diffusion and adsorption properties of the reactant. In order to understand whether the inhibition mechanism of water on diol oxidation in methanol is generally valid, the solvent effect on the aerobic catalytic oxidation of 1,3‐propanediol and its two methyl‐substituted homologues, 2‐methyl‐1,3‐propanediol and 2,2‐dimethyl‐1,3‐propanediol, over a Au/TiO₂ catalyst has been studied here using conventional catalytic reaction monitoring in combination with pulsed‐field gradient nuclear magnetic resonance (PFG‐NMR) diffusion and NMR relaxation time measurements. Diol conversion is significantly lower when water is present in the initial diol/methanol mixture. A reactivity trend within the group of diols was also observed. Combined NMR diffusion and relaxation time measurements suggest that molecular diffusion and, in particular, the relative strength of diol adsorption, are important factors in determining the conversion. These results highlight NMR diffusion and relaxation techniques as novel, non‐invasive characterisation tools for catalytic materials, which complement conventional reaction data.     

Engineering a Small HOMO–LUMO Gap and Intramolecular C−H Borylation by Diborene/Anthracene Orbital Intercalation

The diborene 1 was synthesized by reduction of a mixture of 1,2-di-9-anthryl-1,2-dibromodiborane(4) ( 6 ) and trimethylphosphine with potassium graphite. The X-ray structure of 1 shows the two anthryl rings to be parallel and their π(C₁₄) systems perpendicular to the diborene π(B=B) system. This twisted conformation allows for intercalation of the relatively high-lying π(B=B) orbital and the low-lying π* orbital of the anthryl moiety with no significant conjugation, resulting in a small HOMO–LUMO gap (HLG) and ultimately a C−H borylation of the anthryl unit. The HLG of 1 was estimated to be 1.57 eV from the onset of the long wavelength band in its UV/Vis absorption spectrum (THF, λ_onset=788 nm). The oxidation of 1 with elemental selenium afforded diboraselenirane 8 in quantitative yield. By oxidative abstraction of one phosphine ligand by another equivalent of elemental selenium, the B−B and C¹−H bonds of 8 were cleaved to give the cyclic 1,9-diborylanthracene 9 .     

Iron-Catalyzed Halogen Exchange of Trifluoromethyl Arenes**

The facile production of ArCF₂X and ArCX₃ from ArCF₃ using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C−F bonds. Theoretical calculations suggest direct activation of C−F bonds by iron coordination. ArCX₃ and ArCF₂X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF₂Cl, ArCF₂Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF₂R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents.