Manganese K-Edge X-Ray Absorption Spectroscopy as a Probe of the Metal鈥揕igand Interactions in Coordination Compounds

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• 作者：Michael Roemelt ; Martha A. Beckwith ; Carole Duboc ; Marie-No毛lle Collomb ; Frank Neese ; Serena DeBeer
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：January 2, 2012
• 年：2012
• 卷：51
• 期：1
• 页码：680-687
• 全文大小：526K
• 年卷期：v.51,no.1(January 2, 2012)
• ISSN：1520-510X

文摘

A series of manganese coordination compounds has been investigated by X-ray absorption spectroscopy (XAS). The K-pre-edge spectra are interpreted with the aid of time-dependent density functional theory (TD-DFT). This method was calibrated for the prediction of manganese K-pre-edges with different functionals. Moreover the nature of all observed features could be identified and classified according to the corresponding set of acceptor orbitals, either 1s to 3d transitions or metal-to-ligand charge transfer (MLCT) bands. The observable MLCT bands are further divided into features that correspond to transitions into empty 蟺* orbitals of 蟺-donor ligands and those of 蟺-acceptor ligands. The ability to computationally reproduce the observed features at the correct relative transition energy is strongly dependent on the nature of the transition. A detailed analysis of the electronic structure of a series of Mn coordination compounds reveals that the different classes of observable transitions provide added insight into metal鈥搇igand bonding interactions.