Carbon-Fluorine and Carbon-Oxygen Bond Functionalisation

We are studying catalysts that transform non-reactive molecules containing carbon-oxygen and carbon-fluorine bonds into reactive molecules containing carbon-element bonds (element = B, Al, Zn, Mg). These reactive intermediates may undergo further reactions, forming new carbon-carbon and carbon-heteroatom bonds.

The approach will allow the synthetic diversification of simple ethers and fluorocarbons. Hydrodefluorination and hydrodeoxygenation, the transformation of carbon-fluorine and carbon-oxygen bonds to carbon-hydrogen bonds, are important competitive reactions.


Publications

  • Angew. Chem., Int. Ed. 2012, 51, 12559. pdf
  • Organometallics 2013, 32, 5260. pdf
  • Organometallics 2014, 33, 7027. pdf
  • Chem. Commun. 2015, 51, p15994. open access

Group 3 Catalysts supported by Phosphorus Ligands

The design mold for homogeneous catalysts of rare-earth metals has been set for decades. Catalysts typically incorporate a reactive sigma-bonded substituent and sterically demanding spectator ligands. We recently introduced a group 3 complex that incorporates three elements of ligand design: appended X- and L-type ligands along with reactive sigma-bonded substiutents.



We are studying this complex and related group 3 amides in C-H bond functionalisation and the dehydrogenation of protic and hydridic substrates. We are investigating the role of the supporting ligand in bond activation.

Publications

  • Chem. Commun. 2012, 48, 1745.pdf
  • Chem. Sci. 2013, 4, 691. pdf
  • Chem. Commun. 2014, 50, 9536.pdf
  • Organometallics 2015, 34, 4369. open access

Heterobimetallics in Catalysis

As an undercurrent to our catalytic studies, we are interested in studying the interaction of heavier main group hydrides (M = Al, Zn, Mg) with transition metals. For example, aluminium hydrides have been shown to reversibly coordinate to Zr(IV) and Cu(I) complexes and non-reversibly react with Rh(III) intermediates. We are studying the nature of the bonding in these complexes and not only investigating their role in the catalytic functionalisation of carbon-oxygen and carbon-fluorine bonds but also more broadly in small molecule activation.



Publications