In an effort to reduce the cost of carbon-hydrogen (C-H) bond functionalization, many groups have been made great strides towards employing base metal catalysis. These types of transformations often require high temperatures and catalyst loadings. Our research is using DFT to elucidate high energy transformations and adapt catalytic systems that reduces these barriers, producing more efficient catalysis with base metals. Through the development of a synergistic catalyst design strategy, utilizing both computational modeling and synthetic organometallic chemistry, systems using N-heterocyclic carbene-supported nickel catalysts have been studied and shown to dramatically change reactivity. We have identified a thermodynamic sink along the reaction pathway which can be avoided by modifying the catalytic system, specifically adapting the choice of spectator ligand. Such reactions can be carried out at much lower temperatures and catalyst loadings than previously reported. These results increase the practicality of the wide spread use this type of chemistry.

Addressing high barriers in base metal CH functionalization: Impact of non-innocent ancillary ligands

249th National Meeting (2015)

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