Covalent Bonding of Molecular Catalysts to Metal Oxide Supports via Transesterification Leads to High Loading and Tunable Hybrid Nickel Catalysts

The synthesis, characterization, and structure-function properties for a new class of hybrid catalysts comprised of molecular catalysts covalently bound to metal oxide (MOx) supports via metal-ester bonds is reported. The synthesis of this new class of catalysts is able to achieve targeted and predictable catalyst loading with maximum aerial surface loadings of two uniform, single-site catalysts per nm² of support. X-ray, infrared, and electron paramagnetic spectroscopic characterizations and catalytic reactivity trends show that the MOx support influences the molecular catalyst properties and reactivity through electronic induction effects. The influence of the support on catalytic properties has been correlated to the point of zero charge (PZC) and shown to be predictable. Thus, this class of hybrid catalysts can be tuned by both the structure of the molecular catalyst and by the choice of oxide support. This allows for precise control of the catalyst nucleation, coordination environment, and accessible oxidation states, enabling highly tailored and controllable catalytic properties.