Correlation between Density Functional Studies and Experimental Data of Three New 19-Electron Metal Sandwich Complexes Containing Amido, Ester, and Thioester Cyclopentadienyl Substituents

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• 作者：Samia Kahlal ; Cá ; tia Ornelas ; Jaime Ruiz ; Didier Astruc ; Jean-Yves Saillard
• 刊名：Organometallics
• 出版年：2008
• 出版时间：August 11, 2008
• 年：2008
• 卷：27
• 期：15
• 页码：3693-3700
• 全文大小：272K
• 年卷期：v.27,no.15(August 11, 2008)
• ISSN：1520-6041

文摘

Three 18-electron complexes of the type [CpFe^II(η⁶-C₆Me₆)]⁺ containing an amido, an ester, and a thioester group directly attached to the Cp ring were synthesized and reduced to Fe^I 19-electron complexes. These new 19-electron stable complexes were characterized by UV/vis spectroscopy, showing significant differences in the obtained spectra. In order to better understand the structural and optical properties of the three 19-electron complexes (η⁵-C₅H₄CONHR)Fe^I(η⁶-C₆Me₆), (η⁵-C₅H₄COOR)Fe^I(η⁶-C₆Me₆), and (η⁵-C₅H₄COSR)Fe(η⁶-C₆Me₆), we have carried out DFT calculations on these compounds, as well as on their diamagnetic 18-electron cations [(η⁵-CpCONHR)Fe^II(η⁶-C₆Me₆)][PF₆], [(η⁵-CpCOOR)Fe^II(η⁶-C₆Me₆)][PF₆], and [(η⁵-CpCOSR)Fe^II(η⁶-C₆Me₆)][PF₆] for the sake of comparison. Full geometry optimizations under C₁ symmetry have been carried out on the six complexes, and their optical transitions have been computed on the optimized geometries at the time-dependent DFT (TD-DFT) level. The comparison of the data obtained for the three 19-electron complexes gives us significant information about the influence of the functionalized cyclopentadienyl ring on the electronic structure.