The chemistry of carbon chains
The generation of new molecular structures for use in materials science or pharmaceutically active compounds rests on the assembly molecular structures through chemical synthesis. New synthetic methodologies are therefore in high demand.
In seeking to identify new synthetic approaches, the use of metal-stablised, unsaturated carbon chains (cumulenes) is emerging as an area for development. These species undergo rapid reactions with a variety of electrophilic and nucleophilic reagents, giving products ranging from simple additions to more complex cyclisation and aromatisation processes. However, a more complete map of the reactivity profile associated with these fascinating species remains to be developed.
This project aims to expand the range of linear and quinoidal cumulene complexes based on earth abundant metals (Mn, Fe, Co, Ni) and explore the stoichiomentric transformations of these metal-supported linear, unsaturated carbon chains. The potential to develop this stoichiometric chemistry to catalytic cycles, thereby allowing the facile assembly of complex molecular architectures from simple ligand precursors and a base metal catalyst will also be explored.
Chiral cumulenes have also been predicted to offer unusual ‘helically shaped frontier molecular orbitals, and this project provides a fascinating opportunity to test predictions from these models and explore the optoelectronic properties of these unique compounds.
This project seeks to:
- prepare organometallic complexes in which examples of ‘all-carbon’ chains and closely related ‘carbon-rich’ species feature as ligands;
- explore and map the reactivity profiles of these ligands to uncover new synthetic transformations;
- to explore the redox chemistry, mixed-valence derivatives and electronic structures of these species in close association with studies of their capacity to serve as ‘molecular wires’ and objects to test novel concepts such as helically structured molecular orbitals.
Successful candidates will undertake an exciting program of synthetic chemistry, from the preparation of ligand precursors and metal complexes to the characterisation of reaction products.
The students involved in this project therefore have the opportunity to gain experience in organic and organometallic chemistry, the use of multi-nuclear NMR spectroscopy, mass spectrometry and single-crystal X-ray diffraction.
Students with further interests in physical and computational chemistry will be encouraged to develop skills in electrochemistry, spectroelectrochemistry and DFT calculations.
- M.R. Hall, M. Korb, S.A. Moggach, P.J. Low, Further chemistry of ruthenium alkenylacetylide complexes: routes to allenylidene complexes via a series of electrophilic addition reactions, Organometallics, 2020, 39, 2838 – 2853
- M.R. Hall, R.R. Steen, M. Korb, A.N. Sobolev, S.A. Moggach, J.M. Lynam, P.J. Low, Further evidence for ‘extended’ cumulene complexes: derivatives from reactions with halide anions and water, Chem. Eur. J., 2020, 26, 7226 – 7234
- S. Gückel, J.B.G. Gluyas, S. El-Tarhuni, A.N. Sobolev, M.W. Whiteley, J.-F. Halet, C. Lapinte, M. Kaupp, P.J. Low, Iron versus Ruthenium: clarifying the electronic differences between prototypical mixed-valence organometallic butadiyndiyl-bridged molecular wires, Organometallics, 2018, 37, 1432-1445
- S.G. Eaves, S.J. Hart, A.C. Whitwood, D.S. Yufit, P.J. Low, J.M. Lynam, Rapid Markovnikov addition of HCl to a pendant alkyne: Evidence for a quinoidal cumulene, Chem. Commun. 2015, 51, 9362-9365
- M.I. Bruce, M.Z. Ke, B.D. Kelly, P.J. Low, M.E. Smith, B.W. Skelton, A.H. White, Syntheses of complexes containing substituted 4-ethynylquinolines or 1-azabuta-1,3-dienes by addition of imines to a cationic butatrienylidene-ruthenium complex, J. Organomet. Chem., 1999, 590, 184-201
I am a synthetic chemist, with interests in conjugated compounds and complexes, electrochemistry, charge transfer processes, and determination of the electronic structure of molecular materials. Research in my group ranges from synthetic organometallic chemistry and reactions of complexes with ‘carbon-rich’ ligands, to properties of mixed-valence complexes and the design of compounds for use in the broad field of molecular electronics.
Funding and Collaborations
- 2019 - 2022 ARC Discovery (DP190100074) Molecular transistors: From rings and strings to other things ($420,000)
- 2019 - 2022 ARC Discovery (DP190100073) A radical approach to the design of components for molecular electronics ($438,000)
- Professor Martin Kaupp
- Professor Jean-Francois Halet
- Professor Claude Lapinte
- Professor Frantisek Hartl
- Professor Gemma Solomon
How to Apply
- To be accepted into the Doctor of Philosophy, an applicant must demonstrate they have sufficient background experience in independent supervised research to successfully complete, and provide evidence of English language proficiency
- Requirements specific to this project - Successful candidates will have a good background in synthetic chemistry, and in interest in developing skills in allied areas including electrochemistry, spectroelectrochemistry, and / or DFT calculations
Submit enquiry to research team leader
- Contact the research team leader by submitting an Expression of Interest form via the button below
- After you have discussed your project with the research team leader, contact [email protected] to proceed with your application