Fe L-edge XAS studies of K4[Fe(CN)6] and K3[Fe(CN)6]:: A direct probe of back-bonding
Fe L-edge XAS studies of K4[Fe(CN)6] and K3[Fe(CN)6]:: A direct probe of back-bonding
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DOI：
10.1021/ja061802i
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发表时间：
2006-08-16
影响因子：
15
通讯作者：
Solomon, Edward I.
中科院分区：
文献类型：
--
作者：
Hocking, Rosalie K.;Wasinger, Erik C.;Solomon, Edward I.
两个化合物K-3[Fe（CN）（6）]和K-4[Fe（CN）（6）]在Fe L-边的独特光谱特征已经被确定和表征为由于金属-配体背键而引起的配体π * 轨道的贡献。此外，L-边缘的能量位移和总强度允许在配位场和有效的核电荷的变化被确定。结果表明，配位场项对边能移动起主导作用。实验分析的结果进行了比较，BP 86 DFT计算。计算和实验之间的整体协议是好的，但是，一个更大的差异，在Fe（II）和Fe（III）之间的π反馈量的实验发现。的L-边光谱形状，能量位移和总强度的分析表明，铁L-边X射线吸收光谱提供了一个直接的探针的金属配体的背键。
Distinct spectral features at the Fe L-edge of the two compounds K-3[Fe(CN)(6)] and K-4[Fe(CN)(6)] have been identified and characterized as arising from contributions of the ligand pi* orbitals due to metal-to-ligand back-bonding. In addition, the L-edge energy shifts and total intensities allow changes in the ligand field and effective nuclear charge to be determined. It is found that the ligand field term dominates the edge energy shift. The results of the experimental analysis were compared to BP86 DFT calculations. The overall agreement between the calculations and experiment is good; however, a larger difference in the amount of pi back-donation between Fe(II) and Fe(III) is found experimentally. The analysis of L-edge spectral shape, energy shift, and total intensity demonstrates that Fe L-edge X-ray absorption spectroscopy provides a direct probe of metal-to-ligand back-bonding.