Orientational Self-Sorting in Octahedral Palladium Cages: Scope and Limitations of the " Rule".

Octahedral coordination cages of the general formula [PdL](BF) were obtained by combining [Pd(CHCN)](BF) with heteroditopic N-donor ligands. Four different ligands were employed. These ligands have 3-pyridyl donor groups at one end and 4-pyridyl, imidazolyl, or triazolyl donor groups at the other end.

Construction of Pd-based coordination cages with three geometrically distinct ligands.

Three different dipyridyl ligands were combined with [Pd(CHCN)](BF) to give mixtures of homo- and/or heteroleptic coordination cages. The three ligands were chosen so that one ligand shows a parallel orientation of the coordinate vectors, the second ligand a bent angle of 60°, and the third ligand a bent angle of 120°. We have identified ligand mixtures that give rise to integrative self-sorting, and we have characterized a heterotrileptic [PdLL'L''] cage by single crystal X-ray crystallography.

Difluoro(aryl)(perfluoroalkyl)-λ -sulfanes and Selanes: Missing Links of Trichloroisocyanuric Acid/Potassium Fluoride Chemistry.

The TCICA/KF approach to oxidative fluorination of heteroatoms has emerged as a surprisingly simple, safe, and versatile surrogate to classically challenging fluorination reactions. Although polyfluorination (or chlorofluorination) of diaryl disulfides, diaryl diselenides, diaryl ditellurides, aryl iodides, and aryl(perfluoroalkyl)tellanes has been described, the application of this TCICA/KF methodology to aryl(perfluoroalkyl)sulfanes and selanes remains an area of unexplored chemical space. Accordingly, to address the "missing links" in the developing series of chalcogen-based substrate reactivity, we report mild syntheses of metastable difluoro(aryl)(perfluoroalkyl)-λ -sulfanes and selanes.