We report a rare example of the transformation of HCF3 into a fluoroalkene functional group through defluoroalkylation. We rationalise product formation through DFT calculations, scale-up the synthes...

PhD Project - PhD Studentship in Organometallic Beryllium Chemistry at Imperial College London, listed on FindAPhD.com

Here, the addition of H–H, Be–Be, B–B, and B–H bonds to SnII is studied by experimental and theoretical means. We report the first examples of B–B and Be–Be bond additions to a main group metal centr...

Applicants can apply for any of the following projects (please see application details in the invidual project pdfs). The application deadline is 25...

A series of boron, aluminum, and gallium difluoride complexes [{(ArNCMe)2CH}MF2] (M = B, Al, Ga) are reported as catalysts for the defluorofunctionalization of electron-deficient arenes. Thiodefluorination reactions between TMS–SPh and poly(fluorinated aromatics) proceed under forcing conditions. Evidence is presented for the fluoride entering the catalytic cycle through a metathesis reaction with TMS–SPh to form metal thiolate intermediates, e.g., [{(ArNCMe)2CH}MF(SPh)], which are then nucleophiles for addition to the aromatic substrate, likely through a concerted SNAr mechanism. Attempts to expand the scope of reactivity to include the hydrodefluorination of electron-deficient arenes met with limited success. Activity could, however, be recovered through the addition of NaBArF4 as a catalytic additive (ArF = 3,5-C6H3(CF3)2). NMR titrations suggest that NaBArF4 is capable of coordinating with aluminum and gallium fluoride complexes, most likely through weak M–F---Na interactions (M = Al, Ga), and can play a role in lowering the barrier of metathesis between [{(ArNCMe)2CH}MF2] and Et3SiH to form the group 13 hydrido fluoride [{(ArNCMe)2CH}M(H)F], facilitating catalytic turnover. DFT calculations indicate that this weak interaction leads to a polarization of the M–F bond. The discovery of this additive effect has potentially broad implications in developing new reactivity and applications of thermodynamically stable metal fluorides.

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Aryl aldehydes are key synthetic intermediates in the manufacturing of active pharmaceutical ingredients. They are generated on scale (>1000 kg) through the palladium-catalyzed formylation of aryl bro...