The incorporation of organometallic sites onto pre-treated oxide supports is a strategy to access well-defined heterogeneous catalysts.1 Understanding the nature of the M–OX (OX = surface oxygen) interaction is critical to predict the reactivity of a well-defined organometallic site. For example, the reaction of partially dehydroxylated SiO2 with Cp2ZrMe2 forms Cp2Zr(Me)(OSi≡); a surface species that is inactive in the polymerization of ethylene. However, supporting Cp2ZrMe2 on partially dehydroxylated sulfated oxides (SO) forms [Cp2ZrMe][SO], an electrophilic ion pair that is very active in ethylene polymerization.2 This “support effect,” where functional groups on a support affect speciation on a surface, is very common in heterogenoeus catalysis, and often results in empirical screening of oxides to optimize a catalytic reaction. This presentation will describe our efforts to obtain a molecular description of support effects using solid-state NMR spectroscopy, and recent results describing new weakly coordinating oxide supports that facilitate formation of electrophilic ion-pairs.

Formation of electrophilic ion pairs on oxides: Towards weakly coordinating surfaces

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.