Conventional heterogeneous catalysts are structurally inhomogeneous, providing a multiplicity of transition metal sites that complicate structural and mechanistic analysis. By contrast, the nodes of metal-organic frameworks (MOFs) offer a monodisperse and well-defined coordination environments for transition metals. In this lecture, I show that MOF catalysts prepared by cation exchange are tractable through a range of spectroscopic techniques and can be modeled effectively with molecular complexes. Using these tools, we demonstrate that the local coordination geometry of the MOF node is preserved through cation exchange, representing a predictable metalloligand-like platform for heterogeneous catalysis.  Analyzing the polymerization and oligomerization of light alkenes with these MOFs, we characterize the basis for stereo- and regioselectivity, as well as the mechanisms of activation and deactivation.

Secondary building unit as metalloligand: Structural and mechanistic insight into catalysis at metal-organic framework nodes

254th National Meeting (2017)

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