Mononuclear dioxygen-metal compounds, such as FeO2 complexes with Schiff base and porphyrin ligands, play an essential role in chemistry ranging from oxyhemoglobin to cytochrome P-450 and cytochrome oxidase. It is well known that the superoxo complexes involved in these systems have end-on (?1) coordination geometries with O–O bond lengths of ~1.30 Å, Fe–O–O bond angles of ~135o, and vibrational frequencies of ~1150 cm-1,1 which reflects a formal change of the oxidation state from Mn+ to Mn+1. In addition, there are side-on (?2) peroxospecies, such as [Fe(porphyrin)(O2)]–, in which the O–O bond lengths is ~1.46 Å and vibrational frequencies of ~820 cm-1.1 These reflect a formal change of the oxidation state from Mn+ to Mn+2.
Revised: April 7, 2011 |
Published: June 10, 2008
Citation
Bryantsev V., W.A. De Jong, K.C. Cossel, M.S. Diallo, W.A. Goddard III, G.S. Groenewold, and W. Chien, et al. 2008.Two-Electron Three-Centered Bond in Side-On (?2) Uranyl(V) Superoxo Complexes.Journal of Physical Chemistry A 112, no. 26:5777-5780.PNNL-SA-58627.doi:10.1021/jp804202q