Homoleptic Transition Metal Complexes of the 7-Azaindolide Ligand Featuring 魏1-N1 Coordination

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• 作者：Jacob A. Przyojski ; Monica L. Kiewit ; Kathlyn L. Fillman ; Hadi D. Arman ; Zachary J. Tonzetich
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：October 5, 2015
• 年：2015
• 卷：54
• 期：19
• 页码：9637-9645
• 全文大小：558K
• ISSN：1520-510X

文摘

Homoleptic complexes of the anion of 7-azaindole (AzaIn) were synthesized and characterized for a series of 3d transition metals. For Mn(II), Fe(II), and Co(II), complexes of formula Na₂[M(AzaIn)₄]路2L (L = tetrahydrofuran (THF), 2-MeTHF, toluene, or benzene) were isolated by treatment of the corresponding metal chloride salts with 7-azaindole in the presence of sodium hexamethyldisilazide. The complexes adopt tetrahedral geometries with exclusive coordination to the transition metal ion through the pyrrolic N1 nitrogen atoms of the AzaIn ligands. Solid-state structures of the complexes demonstrate that the sodium cations remain tightly associated with the coordination entities through interaction with both the pyrrolic and pyridine nitrogen atoms of the azaindolide ligands. For Fe(II), replacement of the sodium cations by other alkali metal ions (Li or K) generates new complexes that demonstrate similar coordination geometries to the sodium salts. As a means of comparison, the Fe(II) complex of 4-azaindolide was also investigated. Na₂[Fe(4-AzaIn)₄]路2L adopts a similar solution structure to the 7-azaindolide complexes as judged by NMR spectroscopy and cyclic voltammetry. Density functional theory calculations were performed to investigate the bonding in the 7-azaindolide complexes. Results demonstrate that 7-azaindolide-魏¹-N1 is a nearly pure sigma donor ligand that features a high degree of ionic character in its bonding to mid 3d transition metal ions.