Elucidation of Reaction Mechanisms for Small Molecule Systems
In addition to the focus on large systems and chemical properties, the group maintains an active interest in studying organic and inorganic systems. Generally, the small molecule reactivity projects are carried out in collaboration with experimental collaborators who are world leaders in their respective fields. Specific highlights include:
The novel organic super-electron donors, which have produced extraordinary results in the experimental laboratories of the Murphy group. These compounds have been investigated in order to understand the origin of their selectivity and impressive ability to reductively cleave a variety of challenging substrates (e.g., sulfones, sulfonamides, aryl iodides, etc.).
The group also collaborates with the Mulvey group to work on solving the secrets of synergic synthesis. In these projects we are investigating the manner in which mixed-metal systems are able to work in a synergic way to bring about chemical transformations that are otherwise impossible to achieve. For example, we have recently shown how a Zn-Li based system is achieve multiple C-H/N-H bond activation of a diamine.
The mechanism of hydrosilylation by ruthenium catalysts was carried out at the request of industrial partners (Wacker, GmbH) who sought to understand the mechanism by which ruthenium catalysts operate. After successfully describing the mechanism of three catalysts, a modified catalyst based on our mechanistic investigation was generated and the company subsequently submitted a patent.
The ozonolysis of silanes, germanes and organic substrates involved mechanistic studies to describe the manner in which specific substrates interact with ozone. One of the central themes of the ozonolysis studies, carried out in collaboration with the Plesničar group, was to determine how dihydrogentrioxide could be produced in these reactions – the interaction of ROOOH substrates with Methyltrioxorhenium(IV) (MTO) resulted in the most efficient procedure, currently known, for producing these important polyoxides.