Structure and Nature of the Metal-Ligand Interactions in Mixed Iron(II) Phosphametallocenes
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- 作者：Ê ; nio Dikran V. Bruce and Willian R. Rocha
- 刊名：Organometallics
- 出版年：2004
- 出版时间：October 25, 2004
- 年：2004
- 卷：23
- 期：22
- 页码：5308 - 5313
- 全文大小：138K
- 年卷期：v.23,no.22(October 25, 2004)
- ISSN：1520-6041
文摘
Quantum mechanical calculations at the density functional level (DFT) were carried outin order to analyze the structure and nature of the metal-ligand interactions in mixediron(II) metallocenes of the type Fe(Cp)(L), where L stands for the ligands [C5H5]-, [C4H4P]-,[1,3-P2C3H3]-, and [1,2,4-P3C2H2]-. The nature of the metal-ligand interactions is analyzedby means of the charge decomposition analysis (CDA), in which the extent of donation, back-donation, and repulsive polarization of the electron density, in the region of the bond, isdiscussed in light of the varying number of heteroatoms at the rings. The aromaticity of thefree ligands and the energies involved in the ligand displacement reactions for the process[Fe(Cp)2] + L- 
[Fe(Cp)(L)] + Cp- were also computed and are discussed. Our resultsreveal that changing a CH group of the cyclopentadienyl ligand to phosphorus has the effectof changing drastically the electronic structure of the resulting metallocene and, thus, thereactivity of these compounds.
[Fe(Cp)(L)] + Cp- were also computed and are discussed. Our resultsreveal that changing a CH group of the cyclopentadienyl ligand to phosphorus has the effectof changing drastically the electronic structure of the resulting metallocene and, thus, thereactivity of these compounds.