Mechanochemical synthesis and spectroscopic properties of 1,1′-ferrocenyldiacrylonitriles: the effect of para-substituents

An efficient and simple solvent-free mechanochemical approach for the synthesis of 1,1'-ferrocenyldiacrylonitriles was achieved by grinding together 1,1'-ferrocenedicarboxaldehyde (1) and phenylacetonitriles. A range of 1,1'-ferrocenyldiacrylonitriles and ferrocenylacrylonitriles (2-7) were synthesized within short reaction times, with water as the only by-product. In a similar manner, grinding together ferrocenemonocarboxaldehyde (8) and phenylenediacetonitrile yielded phenylene-3,3'-bis-(ferrocenyl) diacrylonitrile (9) and 3-ferrocenyl-2-(acetonitrophenyl) acrylonitrile (10). The yield and selectivity towards formation of ferrocenyldiacrylonitriles was strongly influenced by the electronegativity of the para-substituent on the phenyl ring of phenylacetonitriles. The compounds were characterized using NMR, IR, and UV-visible spectroscopy and HR-MS. Cyclic voltammetry measurements of selected compounds highlighted the role of ligands in tuning the electrochemical properties of 1,1'-ferrocenyldiacrylonitriles. X-ray crystallographic analysis highlighted the effect of the electronegativity of the para-substituent on the conformation of cyclopentadienyl rings attached to a ferrocenyl moiety.