Publications by authors named "Andrew D Cypcar"
Controlling Hydrogen Evolution and CO Reduction at Transition Metal Hydrides.
Acc Chem Res
December 2024
Article Synopsis
- Fuel-forming reactions like the hydrogen evolution reaction (HER) and CO reduction (COR) are essential for a carbon-neutral economy, with metal hydride intermediates playing a crucial role in these processes.
- The research focuses on controlling hydride reactivity to create selective electrocatalysts operating at low energy costs, examining the free energy changes during catalytic steps and synthesizing intermediates to better understand the process.
- Strategies explored include optimizing hydricity to enhance CO reduction to formate while minimizing unwanted side reactions, as well as designing catalysts that reduce HER rates using electrostatic and steric effects.
High-valent metal oxo complexes are prototypical intermediates for the activation and hydroxylation of alkyl C-H bonds. Substituting the oxo ligand with other functional groups offers the opportunity for additional C-H functionalization beyond C-O bond formation. However, few species aside from metal oxo complexes have been reported to both activate and functionalize alkyl C-H bonds.
View Article and Find Full Text PDFDespite the growing interest in the synthesis of fluorinated organic compounds, few reactions are able to incorporate fluoride ions directly into alkyl C-H bonds. Here, we report the C(sp)-H fluorination reactivity of a formally copper(III) fluoride complex. The C-H fluorination intermediate, CuF, along with its chloride and bromide analogues, CuCl and CuBr, were prepared directly from halide sources with a chemical oxidant and fully characterized with single-crystal X-ray diffraction, X-ray absorption spectroscopy, UV-vis spectroscopy, and H nuclear magnetic resonance spectroscopy.
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