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 (PnX 5 ), tetraphenyl pnictogeniums (PnPh 4 + ), and triphenyl pnictogen tetrachlorocatecholates (PnPh 3 Cat). 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.