Two-Electron Three-Centered Bond in Side-On (η2) Uranyl(V) Superoxo Complexes
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 (η1) 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 (η2) 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.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 936194
- Report Number(s):
- PNNL-SA-58627; 9598; KP1704020; TRN: US0805430
- Journal Information:
- Journal of Physical Chemistry A, 112(26):5777-5780, Vol. 112, Issue 26
- Country of Publication:
- United States
- Language:
- English
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