NMR Spectroscopy as a tool to study homogeneous copper (I) catalysed reactions
(2020)
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- Abstract
- This thesis contributes to the general aim of pushing the boundaries of scientific knowledge a little further in the field of copper chemistry. Here is depicted the use of Nuclear Magnetic Resonance spectroscopy, more specifically 1D 1H and 2D 1H Diffusion-Ordered Spectroscopy, as a tool to elucidate the solution-state nature of copper (I) complexes and to investigate their implication in the reaction mechanism of the catalysed borylation of unsaturated carbon-carbon bonds. The first part is focused on the extrapolation of the molecular sizes of the complexes from their translational self-diffusion in solution, using two different methods (Morris and Williard), both based on the experimental Stokes-Einstein equation describing the Brownian motion of particles in solution and its relationship with the size of these particles. The second part is based on the understanding of the copper (I)-mediated borylation of unsaturated carbon-carbon bonds and of the characterisation of the transient copper (I) complex intermediates of the reaction mechanism. Through a novel and simple out-of-the-glovebox in situ NMR investigation method, the existence of literature-reported structures is confirmed and the identification and characterisation of unprecedented borylcopper (I) alkyl, benzyl, alkenyl and allyl complex intermediates are described. The myriad of reactions and various copper (I) complexes studied in this thesis show the high versatility of this method, and it paves the way for the investigation of many other reaction mechanisms.
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Citations
Payen, R. (2020). NMR Spectroscopy as a tool to study homogeneous copper (I) catalysed reactions. https://hdl.handle.net/2078.5/117659