X-ray spectroscopy as a probe of unique bonding interactions of importance in transition metal catalytic processes

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The specifics of how molecules are held together and how they react depends on a fundamental understanding of their geometric and electronic structure. Using a combination of spectroscopic and computational tools, we seek to provide a detailed understanding of the electronic structure of molecules that are of particular interest due to their unique chemical properties. In this proposal, we seek to explore specific aspects of two major classes of molecular interactions in order to provide a basic framework from which we can understand their chemical behaviour and how they may be used in a number of chemical applications.***Metal π complexes are common intermediates in important academic and industrial catalytic processes. Using a range of spectroscopic approaches, we seek to clearly identify and quantify the importance of π-backbonding in defining the nature of these species. We focus our attention on a series of nickel and copper complexes such that we may exploit x-ray spectroscopic methods to quantify the bonding in these species. Importantly, we seek to correlate these findings with the reactivity of such species so that we may be able to more accurately predict the behaviour of reactive intermediates involving π interactions of this type.***Halogen bonding is an emerging class of chemical interactions that are being used extensively in the synthesis of new materials and for sensor applications. Although such interactions are typically considered to be similar to the more common hydrogen bonding, we have recently determined that these chemical bonds are closer to those observed in transition metal coordination bonds. Given their similarities, we postulate that halogen bonding may compete with coordination bonds to generate highly reactive species. We are therefore exploring the role of halogen bonding in transition metal systems to quantify its effect on both the electronic structure of coordination complexes and their reactivity.