Department of Chemistry

Our research interests focus on understanding the structure, synthesis and reactivity of mixed-metal organometallic compounds and nanocatalysts.

Organometallics for synthesis

We are interested in the activities of molecular organometallic reagents and have used homo- and heterometallics including Li-Al and Li-Zn systems to fabricate hydridic clusters and to function as chemoselective bases. We work on this with Prof Y Kondo (Sendai, Japan), Prof M Uchiyama (Tokyo, Japan) and Prof J Clayden (Manchester). Recent major advances include:

1) the combination of CuCN with organolithium reagents to give bimetallic bases such as (TMP)₂Cu(CN)Li₂.THF (below left) that have applications in C–C bond formation and,

2) the first demonstration that directed benzylic lithiation can be used to generate tertiary carbanions (below right).

Heterogeneous nanocatalysis

The ability to access stable and compositionally and dimensionally controllable metallic nanoparticles promises applications in catalysis. We prepare metal nanoparticles (e.g. Au, Cu, Pd, CuM, PdM, M = Sn, Zn…) and use them to achieve controllably functional surfaces by deposition or encapsulation in mesostructured thin films (illustrated below). In collaboration with Prof J Schouten (Eindhoven) and Prof E Rebrov (Queen's, NI), applications of the resulting microreactors have been developed in the areas of selective hydrogenation, nanotube growth, and fine chemicals synthesis.

We are also interested in fundamental aspects of nanoparticle synthesis and structure. Recently, we have successfully fabricated oxidatively stable Cu-based nanocatalysts as evidenced by XRD and XPS (below). By introducing Zn we have also achieved CuZn nanoparticles with differing intermetallic ratios and predicted upper d-band energies for Cu.

Selected Publications

Deprotonative metalation of chloro- and bromopyridines using amido-based bimetallic species and regioselectivity-computed CH acidity relationships Chem. Eur. J., 2011, 17, 13284

Ligand Effects in the Formation of Tertiary Carbanions from Substituted Tertiary Aromatic Amides Chem. Eur. J., 2011, 17, 8078 (Very Important Paper)

Nanoparticulate PdZn – Pathways towards the synthetic control of nanosurface properties Nanotechnology, 2011, 22, 205701 (Article of Particular Interest)

Nanoparticulate Copper – Routes towards oxidative stability Dalton Trans., 2010, 39, 6496 (Hot paper)

Capillary microreactors wall-coated with mesoporous titania thin film catalyst supports Lab Chip, 2009, 9, 503

Gilman-type versus Lipschutz-type reagents: competition in lithiocuprate chemistry Organometallics, 2009, 28, 38

Mixed alkyl-amido aluminate as kinetically controlled base J. Am. Chem. Soc., 2008, 130, 16193