ABSTRACT
The use of new dynamic scaffolds for constructing inorganic and organometallic complexes with enhanced reactivities is an important new research direction. Toward this fundamental aim, an improved synthesis of the dynamic scaffold selenanthrene, along with its monoxide, trans-dioxide and the previously unknown trioxide, is reported. A discussion of the potential reaction mechanism for selenanthrene is provided, and all products were characterized using 1H, 13C, and 77Se nuclear magnetic resonance (NMR) spectroscopy and single-crystal X-ray crystallography. The dynamic ring inversion processes (i.e., "butterfly motion") for selenanthrene and its oxides were investigated using variable-temperature 1H NMR and density functional theory calculations. The findings suggest that selenanthrene possesses a roughly equal barrier to inversion as its sulfur analogue, thianthrene. However, selenanthrene oxides evidently possess larger inversion barriers as compared to their sulfur analogues due to the enhanced electrostatic intramolecular interactions inherent between the highly polar selenium-oxygen bond and adjacent C-H moieties. Finally, we propose a quantitative "flexibility index" in deg/(kcal/mol) for various tricyclic scaffolds to provide researchers with a comparative scale of dynamic motion across many different systems.
