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Methods of Ex Situ and In Situ Investigations of Structural Transformations: The Case of Crystallization of Metallic Glasses
Published on: June 7, 2018
A structural analysis of {M4O4} cubanes where M = Mn and Fe
1Department of Inorganic Chemistry, University of Geneva, 30 quai Ernest Ansermet, CH 1211, Geneva 4, Switzerland. Alan.Williams@chiam.unige.ch
Abstract:
The structures of the M4O4 units found in manganese and iron cubanes are analysed. The model used is that established previously for cobalt and nickel cubanes based on a distortion of the cube by compression of the oxygen atoms along a body diagonal. Further distortion which maintains a S4 or, less frequently, a C3 axis is generally seen. In spite of the distortion, average M-M distances in a cubane are quite constant for a given oxidation state and generally decrease as the metal is oxidised. The angles at the oxygen atoms increase from 90 degrees for the ideal cube to around 97 degrees . For metal oxidation states above or equal to +iii micro3-hydroxo ligands transform to micro3-oxo ligands. Ligands such as carboxylates which can bridge diagonal faces of the cube are generally seen with higher oxidation states.
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