Ligand dissociation is perhaps the single most common reaction step in organometallic chemistry. Barriers to ligand dissociation are typically considered in terms of metal-ligand Bond Dissociation Enthalpy or Energy (BDE); these, however, are thermodynamic properties The factors that govern the rates of ligand dissociation, other than these thermodynamic components, are not well explored. In the course of our study of the regioselectivity of catalytic alkane dehydrogenation by pincer-iridium complexes, it was concluded that the kinetic barrier to the dissociation of the olefin product is the rate-determining step in the case of some - but not all - such catalysts. In that context, we have begun a computational and experimental study of the rates of dissociation of simple ligands (e.g. phosphines) from isomers of related complexes in an effort to elucidate the non-thermodynamic factors that govern metal-ligand bond dissociation rates.

Investigation of the non-thermodynamic factors governing metal-ligand bond dissociation rates

254th National Meeting (2017)

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