Our main research interests are in the synthesis,
structure, bonding and reactivity of new organometallic and coordination
compounds of the p-block elements (i.e. s-block, p-block, d0
and d10
compounds). We aim
to utilise the highly reactive nature of “non-transition” metal
organometallics in the targeted syntheses of novel reagents. We then seek to
explore the wealth of fascinating structures and bonding patterns adopted by
these species and investigate any potential applications they may have (e.g., as
ligands towards a range of metals, as catalysts and as precursors to new
materials). The title of our research project serves to emphasise that we seek
to understand and control the way in which molecular architectures are built up.
Two case studies serve to illustrate the flavour of this work:
Low-coordinate phosphorus
The substitution of CH units for isolobal P centres is a trivial paper exercise but one which is far more difficult to execute in the laboratory. Research (by others) over the past 3 decades has developed routes to low coordinate phosphorus compounds and explored their chemistry, with application as new material sand as novel ligands for catalysis. Indeed the depth of this work has led to phosphorus being coined a carbon copy. Our own twist on this story has involved developing novel low-coordinate phosphorus species which is illustrated using two distinct examples. Firstly, we reported the first example of
a cationic phosphorus/carbon cluster that is isoelectronic with the
anti-aromatic cyclopentadienyl cation [C5R5]+. More recently, we have used using fascinating low-coordinate phosphorus molecules, e.g., 2,4,6-tritertbutyl-1,3,5-triphosphabenzene, as templates for the development of new molecular architectures. In particluar we reason that the weakness of CP bonds relative to homonuclear CC bonds leads to a lower HOMO-LUMO gap in similar bodning regimes and reactivity more akin to that associated with transition metals raher than main group systems.
Gold
Traditionally thought of as a noble metal, the chemistry of gold was relatively undeveloped, but the observation that gold nanoparticles can be exceptionally active catalysts has spurred a great amount of research. Indeed gold now fascinates materials scientists, catalysis, surface and synthetic chemists and theoreticians alike. Further developments of gold(I) catalysed chemistry depend to a degree on developing a detailed understanding of the related topics of structure and bonding, and of course mechanism. We have developed a number of different ways of stabilising gold alkene and gold alkyne complexes species which add detail to the understanding of these fundamental interactions. Furthermore we have applied this insight in the application of gold catalysts in oxidative direct arylation, a potentially powerful way of making biaryls where the critical C-C bond forming step is facilitated by gold under mild conditions and which tolerates a diverse decoration of functionality on the substates.
A project in this
group would provide a wide training base: organic synthesis (ligand design,
preparation and purification), inorganic synthesis (transition metal and main
group complexes, handling of extremely air- and moisture-sensitive compounds by
high-integrity schlenk line and glove-box techniques), spectroscopy (NMR, IR),
single crystal X-ray diffraction, literature awareness (journals, Beilstein/Gmelin/BIDS/CSD
databases etc.) and computational studies. For further details please see
the references below.
References
A full list of Publications are available on this website. For some specific papers illustrating the above we've selected the following:
Angew. Chem., Int .Ed. Engl., 2003, 42, 2778 (rated as a Very Important Paper).
Chem. Commun., 2009, 3877-3879 (rated as a Hot Paper)
Angew. Chem. Int. Ed., 2011, 50, 7592 (rated as a Very Important Paper).
Science, 2012, 337, 1644
Angew. Chem. Int. Ed., 2013, 52, 3481
J. Am. Chem. Soc. 2014, 136, 254 ( featured in JACS Spotlight)