Synthesis, structures and spectroelectrochemistry of methyl-substituted bis(η5-indenyl)iron(II) complexes

Several new methyl-substituted indenyl ferrocenes were prepared by metathesis reactions of the indenide (generated from the appropriate indene with BuLi) with ferrous chloride. The indenides used to prepare new ferrocenes were: 2-methyl-, 1,2-dimethyl-, 4,7-dimethyl-, 1,4,7-trimethyl-, and 1,3,4,7-tetramethyl-indenide. These indenyl ferrocenes, along with those prepared from indenide, 1-methylindenide, and 1,3-dimethylindenide, were then characterized by 1H and 13C NMR, UV/visible spectroscopy, cyclic voltammetry and mass spectrometry. The cyclic voltammetry showed an additive relationship between oxidation potential and the number of methyl groups which is also position-dependent, whereas the UV/visible spectra showed two absorptions essentially unaffected by methyl substitution. Additionally, bis(2-methylindenyl)iron(II) and bis(4,7-dimethylindenyl)iron(II) were characterized by X-ray crystallography.

Graphical abstractSeveral methyl-substituted indenyl-ferrocene complexes were prepared and then characterized by NMR and UV/visible spectroscopy, as well as by cyclic voltammetry. Oxidation potentials, but not UV/visible spectra, were found to be dependent on the degree of methyl substitution and the substitution pattern. Some ferrocenes were also crystallographically characterized.Figure optionsDownload full-size imageDownload as PowerPoint slide