Otero E, Wilks R G, Regier T, Blyth R I R, Moewes A, Urquhart S G
Department of Chemistry, University of Saskatchewan, 110 Science Place, Saskatoon, Saskatchewan, Canada.
J Phys Chem A. 2008 Jan 31;112(4):624-34. doi: 10.1021/jp074625w. Epub 2008 Jan 9.
The iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3)5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hückel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.
报道了取代二茂铁化合物（Fe(Cp-(CH3)5)2、Fe(Cp)(Cp-COOH)、Fe(Cp-COOH)2和Fe(Cp-COCH3)2）的铁2p和碳1s近边X射线吸收精细结构（NEXAFS）光谱，并借助扩展休克尔分子轨道（EHMO）理论和密度泛函理论（DFT）对其进行了解释。在铁2p和碳1s NEXAFS光谱中均观察到显著的取代基效应。这些效应可能与环戊二烯基配体及其取代基的供电子/吸电子性质以及环戊二烯基配体与不饱和取代基之间π*共轭的存在有关。
