Preparation and reactivity of unsupported nickel-lewis acid complexes

The transition metal-catalysed borylation of organic substrates is a key synthetic tool for the preparation of complex molecules, as the resulting boronic acids can be used in C-C bond forming reactions. Whilst the use of precious metals for this reactivity has been well established economic and environmental imperatives have led to renewed efforts in the use of the first-row transition metals for bond activation and catalysis. There are now a number of reports of nickel-catalysed borylation reactions, but only a handful of structurally characterised Ni-boryl complexes have been reported in the literature. We recently reported (Chem. Commun., 2024, 60, 874) the first examples of unsupported Ni-boryls being formed through complete oxidative addition of a B-X bond, and identified the dependence of this reactivity on the identity of X in the B-X bond (X = H or Cl).

With straightforward access to well defined Ni-boryl species, this project will systematically investigate their reactivity towards small molecules, with a view to translating this reactivity into new catalytic transformations. The project will also investigate synthetic approaches for preparing new complexes featuring covalent bonds between a nickel centre and a Lewis acid, to extend reactivity beyond nickel-boryl complexes.

The successful candidate will receive training in a range of techniques applicable to synthetic organometallic chemistry including the manipulation of air and moisture sensitive compounds, multinuclear NMR, mass spectrometry and X-ray diffraction. In addition to developing practical skills the student will also develop excellent reasoning and presentation skills.

Open to any UK or international candidates. Up to 30% of our UKRI funded studentships can be awarded to candidates paying international rate fees.

You will need to meet the minimum entry requirements for our PhD programme.