Dutton - Organic, organometallic and inorganic chemistry from synthetic and theoretical perspectives
We examine the fundamental chemistry of a wide variety of systems (literally spanning the periodic table from beryllium to iodine) using both synthetic and computational theoretical approaches.
Our broad approach is to discover new structure, bonding and reactivity for a variety of elements by placing those elements into unusual bonding environments and carefully observing what they do. To achieve this we target reactions that result in either very electron poor or very electron rich environments.
Complementing the synthetic work, detailed theoretical studies are also employed to both understand our observations and predict new chemistry. Our research has been published in such journals as The Journal of The American Chemical Society and Angewandte Chemie, and we are currently funded by the Australian Research Council.
Development of new hypervalent iodine based oxidants and their use in “inorganometallic chemistry”
Iodine typically prefers an oxidation state of -1 as iodide or +1 in normal organoiodine compounds such as PhI. In this project we aim to generate cationic iodine coordination complexes where the oxidation state of iodine is +3. The high oxidation state of iodine coupled with the cationic nature of the complexes renders these compounds very strong oxidizing agents.
We use these complexes to generate highly charged transition metal and main group coordination compounds in a single step. These cations have potential use in catalytic transformations through C-H activation. For an example of our work on synthesizing a new family of gold complexes using this strategy, see Corbo et al., 2014.
Discovering new organic chemistry using an inorganic touch
The invention of new organic chemical reactions and novel classes of organic compounds is a challenging but critical area in synthetic chemistry. We are primarily inorganic chemists, however using a philosophy of simple viewing carbon as another main group metal chemistry will allow us to unlock new organic chemistry. For example, we are using CO as a labile ligand to stabilize the otherwise unattainable perfluorinated trityl cation and targeting the long sought after cyclopentadienyl cation by trying to "fool" the central carbon atom into thinking it is a boron (Iverson et al., 2014). In another project (funded by an ARC DECRA) we are using N-heterocyclic carbene ligands to stabilize small carbon fragments such as C2 and C3, then attempting to utilize these carbon coordination complexes as synthetic sources of those fragments.
Beryllium chemistry the safe way and other computational chemistry
Beryllium is predicted to have the richest chemistry of the alkaline earth metals (group 2), owing to its relatively high electronegativity. This chemistry is underdeveloped as most Be containing molecules are too toxic to handle under reasonable laboratory conditions. Be, however, has few electrons with a predictable electronic nature and this makes it very attractive for theoretical studies using computational methods.
We have predicted several new reactions/molecule classes for Be, and have even seen some of our predictions realized by chemists who can safely handle Be. We are currently exploring the very fertile ground of potential new chemistry in organoberyllium chemistry via computational methods. We also look at the mechanisms of interesting new organometallic reactions reported in the literature for a wide variety of elements, for example, the activation of N-heterocyclic carbenes by element hydrides (Iverson et al., 2013).