Exploring the Effects of Se Basicity on a Te···Se Interaction Supported by a Rigid Indazolium Backbone.

With an interest in chalcogen bonding, we use a rigid indazolium backbone to install a formally zero-valent Se center next to a divalent Te center, allowing us to investigate the effects of oxidation of the Se center on the observed Te···Se interaction. Through spectroscopic and computational comparison of the Se(0) species with its Se(II) counterpart and their monochalcogen analogues, we experimentally and computationally investigate the effect of modulating Se basicity on the resulting Te···Se interaction. Comparison with well-studied naphthalene and acenaphthene variants indicates that the increased basicity of the Se(0) center allows for a comparably strong Te···Se interaction despite longer peri distances and a larger splay angle. Finally, our study illuminates the potential non-innocence of cationic organic substituents in chalcogen-bonding catalysis of the transfer hydrogenation of quinolines.

Analyzing Fluoride Binding by Group 15 Lewis Acids: Pnictogen Bonding in the Pentavalent State.

We report the results of a computational investigation into fluoride binding by a series of pentavalent pnictogen Lewis acids: pnictogen pentahalides (PnX5), tetraphenyl pnictogeniums (PnPh4+), and triphenyl pnictogen tetrachlorocatecholates (PnPh3Cat). Activation strain and energy decomposition analyses of the Lewis adducts not only clearly delineate the electrostatic and orbital contributions to these acid-base interactions but also highlight the importance of Pauli repulsion and molecular flexibility in determining relative Lewis acidity among the pnictogens.

Synthesis of an Indazole/Indazolium Phosphine Ligand Scaffold and Its Application in Gold(I) Catalysis.

Advances in ligand development have allowed for the fine-tuning of gold catalysis. To contribute to this field, we designed an indazole phosphine ligand scaffold that allows facile introduction of cationic charge through methylation. With minimal changes to the structure upon methylation, we could assess the importance of the electronic effects of the insertion of a positive charge on the catalytic activity of the resulting gold(I) complex. Using the benchmark reactions of propargyl amide cyclization and enyne cyclization with and without hexafluoroisopropanol (HFIP), we observed marked differences in the catalytic activities of the neutral and cationic gold species.

Augmenting metallobasicity to modulate gold hydrogen bonding.

We report the synthesis and characterization of two phosphine gold carbinol species designed to support intramolecular Au⋯H-O hydrogen bonding. Increasing the metallobasicity of gold through chloride to phenyl ligand substitution produced an observable increase in this hydrogen bond's strength which was analyzed experimentally and computationally.