Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis.

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside a variety of other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these interactions in catalyst designs that also incorporate a reactive transition metal. In isolation, a single ionic interaction exhibits low directionality, but in many successful systems they exist alongside additional interactions which can provide a high degree of organization at the selectivity-determining transition state. Even in situations with a single key interaction, low directionality is not always detrimental, and can even be advantageous, conferring generality to a single catalyst. This Review explores design approaches that utilize ionic interactions to control selectivity in transition metal catalysis. It is divided into two halves: in the first, the ionic interaction occurs in the outer sphere of the metal complex, using a ligand which is charged or bound to an anion; in the second, the metal bears a formal charge, and the ionic interaction is with an associated counterion.