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Defining the Electronic Structure of Transition Metal Singlet Dioxygen Adducts

Principal Investigator: 

Rhodium(I) complexes generally bind dioxygen through oxidative addition to form stable Rh(III) peroxo complexes. In collaboration with Cathy Crudden at Queen's University, we recently reported a series of stable square planar Rh(I) complexes which behave very differently in the presence of dioxygen - the products of oxygenation remain square planar and O2 binds side-on while keeping a very short O-O bond distance. Using a combination of computational and spectroscopic methods, we have determined that these represent a previously undiscovered class of metal dioxygen complexes: singlet dioxygen adducts. we are presently exploring the nature of the bonding in these species and determining its impact on reactivity.

See Praetorius et al, JACS 2008Cipot-Weshler et al, Organomet 2012; and Keske et al, Dalton Trans 2013 for more details.

[We are currently seeking a student to pursue some of these investigations]