화학공학소재연구정보센터
Inorganic Chemistry, Vol.45, No.13, 4910-4913, 2006
Theoretical evidence favoring true iron(V)-oxo corrole and corrolazine intermediates
Although many formally Fe( V) intermediates are known in the form of peroxidase compound I intermediates and their synthetic models, "true" d(3) (FeO)-O-V intermediates have remained elusive and hence a Holy Grail of sorts for many bioinorganic chemists. Very recently, Newcomb and co-workers provided transient absorption spectroscopic evidence suggestive of (FeO)-O-V corrole intermediates. Here, we report DFT calculations predicting nearly isoenergetic (FeO)-O-V and (FeO)-O-IV corrolato(2-.) states for Fe(corrolato)( O) intermediates. In the course of a theoretical search for systems in which a true (FeO)-O-V state might be favored by a clear and substantial margin of energy, we have identified corrolazine as a promising supporting ligand; thus, we find that with corrolazine, the FeVO states are favored by at least 0.5 eV over (FeO)-O-IV corrolazinato(2-.) states.