This project involves the synthesis and structural characterisation of a number of different metallocenes and half-sandwich complexes of Groups IV-VII transition metals that bear a borylcyclopentadienyl ligand (Cp(B) = C5H4-B(C6X5)3 X= F or Cl) or a silylcyclopentadienyl ligand (Cp(Si) = C5H4-SR3) or combinations of both. Whilst some of these compounds are known [1-4] their electrochemical behaviour is almost entirely unexplored and will be addressed by this project. We seek to exploit the redox chemistry of the metal centre in combination with the Lewis acidity of the pendant boryl unit for the electrochemical small molecule activation of various organic substrates. This groundbreaking approach has a number of exciting potential applications. Within the School of Chemistry and the Wildgoose group there exist excellent facilities for molecular characterisation of synthetic products (including a modern NMR suite, X-ray crystallography and mass spectrometry services) and electrochemical equipment and simulation software. Highly motivated candidates are sought who have some experience/interest in inert-atmosphere synthesis. Experience of electrochemistry (cyclic voltammetry) is desirable but not essential. The student will be trained in both inert atmosphere synthetic manipulations on Schlenk lines and in gloveboxes, and also in quantitative electrochemical techniques such as cyclic voltammetry and digital simulation of voltammograms to extract mechanistic and kinetic information. Together, these represent an opportunity to acquire a rare and valuable combination of skill sets in both areas of synthetic chemistry and electrochemistry.

Lancaster, S. J.; Hughes, D. L. Dalton Trans 2003, 1779–1789

Aldridge, S.; Bresner, C. Coordination Chemistry Reviews 2003, 244, 71–92

Lancaster, S. J.; Bochmann, M. Organometallics 2001, 20, 2093–2101

Lancaster, S. J.; Al-Benna, S.; Thornton-Pett, M.; Bochmann, M. Organometallics 2000, 19, 1599–1608.