Ferrocene-based Amides, Amines and Alcohols as a Platform for the Design and Synthesis of Redox-active Hybrids: Synthesis, Electrochemical and Computational Studies

Abstract

Herein we report on the synthesis and characterization of a number of the simplest ferrocenes, namely Fc-amides (4a-i), Fc-amines (5a-i) and Fc-alcohol (1), as starting materials for the synthesis of redox-active ferrocene-modified compounds. Suitable conditions allowed preparing a seria of various ferrocenes with aliphatic and aromatic substituents in good to high yields. The title products were characterized by 1H, 13C NMR, IR, ESI-MS analytical methods. The structure of ferrocenyl(ortho-chlorophenyl) methanol (1) was determined by single-crystal X-ray diffraction. Geometrical parameters in compound 1 were calculated using the ab initio MP2/6-31G* method and based on the advanced DFT calculations, DFT wb97xd/6-31G* and DFT wb97xd/6-311+G*. Electrochemical investigations by cyclic voltammetry revealed reversible redox processes for the ferrocenyl amides. Potentials were also calculated using two basis sets, 6-31G* and 6-311+G*, and demonstrated a high degree of correlation with experimental results.