Effects of surface acidity on the structure of organometallics supported on oxide surfaces.

Well-defined organometallics supported on high surface area oxides are promising heterogeneous catalysts. An important design factor in these materials is how the metal interacts with the functionalities on an oxide support, commonly anionic X-type ligands derived from the reaction of an organometallic M-R with an -OH site on the oxide. The metal can either form a covalent M-O bond or form an electrostatic M + ⋯ - O ion-pair, which impacts how well-defined organometallics will interact with substrates in catalytic reactions. A less common reaction pathway involves the reaction of a Lewis site on the oxide with the organometallic, resulting in abstraction to form an ion-pair, which is relevant to industrial olefin polymerization catalysts. This Feature Article views the spectrum of reactivity between an organometallic and an oxide through the prism of Brønsted and/or Lewis acidity of surface sites and draws analogies to the molecular frame where Lewis and Brønsted acids are known to form reactive ion-pairs. Applications of the well-defined sites developed in this article are also discussed.