Electronic Effects in 4-Substituted Bis(imino)pyridines and the Corresponding Reduced Iron Compounds

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• 作者：Jonathan M. Darmon ; Zo毛 R. Turner ; Emil Lobkovsky ; Paul J. Chirik
• 刊名：Organometallics
• 出版年：2012
• 出版时间：March 26, 2012
• 年：2012
• 卷：31
• 期：6
• 页码：2275-2285
• 全文大小：512K
• 年卷期：v.31,no.6(March 26, 2012)
• ISSN：1520-6041

文摘

A family of 4-substituted bis(imino)pyridines, 4-X-^iPrPDI (4-X-^iPrPDI = 2,6-(2,6-ⁱPr₂-C₆H₃N鈺怌Me)₂-4-X-C₅H₂N; X = CF₃, ^tBu, Bn, NMe₂), has been synthesized and the iron coordination chemistry studied. Sodium amalgam reduction of the iron dihalides (4-X-^iPrPDI)FeX₂ (X = Cl, Br) in the presence of excess carbon monoxide furnished the corresponding iron dicarbonyl compounds (4-X-^iPrPDI)Fe(CO)₂. Equilibrium mixtures of the four- and five-coordinate iron dinitrogen compounds (4-X-^iPrPDI)FeN₂ and (4-X-^iPrPDI)Fe(N₂)₂ were prepared by performing the sodium amalgam reduction of the iron dihalides under a dinitrogen atmosphere. Electrochemical and spectroscopic measurements were conducted on the free ligands and the iron derivatives to systematically evaluate the influence of each para pyridine substituent on the electronic structure of the compound.