In a collaboration that extends back to 1987 the Que and Munck groups have studied a variety of high-valent iron complexes. Using Mössbauer and EPR  spectroscopy, combined with density functional theory,  we have characterized novel S = 1/2  Fe(V)=O ,  S = 1 and S = 2 Fe(IV)=O complexes, as well as a variety of high-valent dinuclear Fe(IV)Fe(IV) and Fe(III)Fe(IV) systems. Quite interestingly, the TPA ligand has yielded four distinct oxo-bridged diiron(IV) complexes, and in addition an Fe(III)Fe(IV) complex for which superexchange interactions cause a spin transition at the Fe(IV) site from S = 1 to S = 2. The transition to high-spin dramatically increases H-bond cleavage and oxo-transfer reactivities. As high-valent oxidation chemistry rarely yields pure species, a variety of spectroscopic tricks had to be employed to prepare the spectra of the species of interest.<br/>

Mössbauer, EPR and DFT studies of Fe(V)=O, Fe(IV)Fe(IV) and Fe(III)<sup> </sup>Fe(IV) complexes of biological relevance

253rd National Meeting (2017)

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Mössbauer, EPR and DFT studies of Fe(V)=O, Fe(IV)Fe(IV) and Fe(III) Fe(IV) complexes of biological relevance

Mössbauer, EPR and DFT studies of Fe(V)=O, Fe(IV)Fe(IV) and Fe(III)Fe(IV) complexes of biological relevance