Trifluoromethylated selenoethers are quite rare despite their potential and the interest that they generate. A series of trifluoromethylseleno derivatives, either primary and secondary aliphatic or aromatic and heterocyclic, is described herein by the reaction of easily prepared organic selenocyanates and CuCF3. Another beneficial feature of this reaction is the use of fluoroform as a source for the CF3 group, a compound whose chemistry is currently being intensively researched because it is a potent greenhouse gas that should not be released into the atmosphere.

A series of diphosphine Pt(II) aryl iodo complexes were reacted with XeF(2) to cleanly produce the corresponding Pt(II) difluoro complexes and free iodoarenes. However, when aryl ligands bearing fluoro substituents in the ortho positions were used, the formation of the corresponding Pt(II) aryl fluoro complexes was observed in the reaction with XeF(2). In the case of the Pt-C(6)F(5) complex, the products of the fluoride-for-iodide exchange were the only products observed by means of (31)P and (19)F NMR spectroscopy. The experimental and theoretical studies suggest that the formation of iodine-fluorine bond may accompany this transformation. The plausible "I-F" species could be trapped by electron-richer organoplatinum complexes to give a Pt(IV) transient which subsequently eliminates the corresponding aryl iodide. Hence, in some cases a pathway involving an attack of XeF(2) at the iodo ligand of Pt(II) aryl iodo complexes to generate I-F species can be operative in addition to or instead of the XeF(2) attack at the metal center. Our DFT studies demonstrate that the electrophilic attacks of XeF(2) at both sites, platinum and iodide, can be competitive.

The quest for obtaining conjugated oligothiophene-containing molecules with narrower HOMO-LUMO gaps and higher oxidation and reduction potentials is the subject of this study. Molecules containing the bithiophene tetraoxide (2) and the terthiophene hexaoxide (3) moieties were prepared and studied. They were obtained by transferring oxygen atoms to the corresponding dibromo oligothiophenes with the HOF⋅CH3CN complex and then cross-coupling them with either thiophene- or acetylene tin derivatives. The photophysical and electrochemical studies of the products revealed that this particular class of mixed thiophenes is characterized by significantly smaller frontier orbital gaps and higher oxidation and reduction potentials compared with any other arrangement of oligothiophenes including various [all]-S,S-oxygenated thiophene derivatives.

A general route for the preparation of selenones (R2SeO2) is presented. This task is achieved through the quick and high‐yielding reaction of selenides (R2Se) with HOF·CH3CN. The reaction tolerates some elusive electron‐deficient and sterically hindered selenides. Some mechanistic aspects are also investigated and discussed.

Star-shaped oligothiophenes are promising materials for applications in the organic electronics field. For the first time, a range of star-oligothiophenes was oxidized to the corresponding all-S,S-dioxides by using the HOF·CH(3)CN complex. These materials exhibit considerable thermal stability and red-shift absorptions in the UV/vis relative to the parent compounds.