有机金属钌配合物的钌K边X射线吸收光谱中预边特征的归属
Assignment of Pre-edge Features in the Ru K-edge X-ray Absorption Spectra of Organometallic Ruthenium Complexes.
作者信息
Getty Kendra, Delgado-Jaime Mario Ulises, Kennepohl Pierre
机构信息
Department of Chemistry, The University of British Columbia, Vancouver BC, Canada V6T 1Z1.
出版信息
Inorganica Chim Acta. 2008 Mar 1;361(4):1059. doi: 10.1016/j.ica.2007.07.029.
Abstract
The nature of the lowest energy bound-state transition in the Ru K-edge X-ray Absorption Spectra for a series of Grubbs-type ruthenium complexes was investigated. The pre-edge feature was unambiguously assigned as resulting from formally electric dipole forbidden Ru 4d<--1s transitions. The intensities of these transitions are extremely sensitive to the ligand environment and the symmetry of the metal centre. In centrosymmetric complexes the pre-edge is very weak since it is limited by the weak electric quadrupole intensity mechanism. By contrast, upon breaking centrosymmetry, Ru 5p-4d mixing allows for introduction of electric dipole allowed character resulting in a dramatic increase in the pre-edge intensity. The information content of this approach is explored as it relates to complexes of importance in olefin metathesis and its relevance as a tool for the study of reactive intermediates.
摘要
研究了一系列格拉布型钌配合物在Ru K边X射线吸收光谱中最低能量束缚态跃迁的性质。预边特征被明确归因于形式上电偶极禁阻的Ru 4d<--1s跃迁。这些跃迁的强度对配体环境和金属中心的对称性极为敏感。在中心对称配合物中，预边非常弱，因为它受弱电四极强度机制的限制。相比之下，当打破中心对称性时，Ru 5p - 4d混合允许引入电偶极允许的特性，导致预边强度急剧增加。探讨了该方法与烯烃复分解中重要配合物相关的信息内容及其作为研究反应中间体工具的相关性。
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