Preparation and synthetic applications of aryl tetraflates (ArOSO2CF2CF2H).

We have recently developed an improved synthetic route to 1,1,2,2-tetrafluoroethanesulfonic acid (HCF2CF2SO3H, TFESA) and explored the applications of this newly available superacid in catalysis. Low volatility, ease of handling, and a convenient 1H NMR handle make this acid an attractive alternative to triflic acid. TFESA can also be converted to several of its derivatives: anhydride, sulfonyl chloride, and sulfonyl fluoride, which provide a good entry point for the synthesis of aryl sulfonates.

Photoinduced charge transfer mediated by DNA-wrapped carbon nanotubes.

We report our observation of solution photochemical reactions catalyzed by carbon nanotubes. Addition of sub-millimolar Ag+ ions into a solution of DNA-wrapped carbon nanotubes (DNA-CNT) leads to a strong charge-transfer band in the UV region of the optical absorption spectrum. Light irradiation of the Ag+/DNA-CNT mixture results in reduction of Ag+ to Ag nanoparticles and concomitant oxidation of water.

Copper(I)-catalyzed synthesis of azoles. DFT study predicts unprecedented reactivity and intermediates.

Huisgen's 1,3-dipolar cycloadditions become nonconcerted when copper(I) acetylides react with azides and nitrile oxides, providing ready access to 1,4-disubstituted 1,2,3-triazoles and 3,4-disubstituted isoxazoles, respectively. The process is highly reliable and exhibits an unusually wide scope with respect to both components. Computational studies revealed a stepwise mechanism involving unprecedented metallacycle intermediates, which appear to be common for a variety of dipoles.

Structural and mechanistic investigations of the oxidation of dimethylplatinum(II) complexes by dioxygen.

The oxidation of (tmeda)Pt(II)(CH(3))(2) (1, tmeda = N,N,N',N'-tetramethylethylenediamine) to (tmeda)Pt(IV)(OH)(OCH(3))(CH(3))(2) (3) by dioxygen in methanol proceeds via a two-step mechanism. The initial reaction between (tmeda)Pt(CH(3))(2) and dioxygen yields a hydroperoxoplatinum(IV) intermediate, (tmeda)Pt(OOH)(OCH(3))(CH(3))(2) (2), which reacts with a second equivalent of (tmeda)Pt(CH(3))(2) to afford the final product 3. Both 2 and 3 have been fully characterized, including X-ray crystallographic structure determinations.