Synthesis and molecular structures of S-2-FcNHCOC6H4SH and [MIII(OEP)(S-2-FcNHCOC6H4)] (Fc = ferrocenyl, M = Fe, Ga): Electrochemical contributions of intramolecular SH⋯OC and NH⋯S hydrogen bonds

A novel redox-active thiolate ligand having a ferrocene moiety, S-2-FcNHCOC6H4SH (1a), and its porphyrin-thiolate compounds, [MIII(OEP)(S-2-FcNHCOC6H4)] (M = Fe (2a), Ga (3a)) were synthesized and characterized by X-ray analysis, spectroscopic and electrochemical measurements. The corresponding 4-substituted derivatives (1b–3b) were also synthesized to estimate the contribution of substituent effects. The formation of intramolecular SH⋯OC or NH⋯S hydrogen bonds in solution was established by 1H NMR and IR spectra. The cooperative effects of the hydrogen bonds and π-conjugation were found on redox potentials of Fc and iron-porphyrin moieties.

Graphical abstractA novel redox-active thiolate ligand having a ferrocene moiety, S-2-FcNHCOC6H4SH, and its porphyrin-thiolate compounds, [MIII(OEP)(S-2-FcNHCOC6H4)] (M = Fe, Ga) were synthesized and characterized by X-ray analysis, spectroscopic and electrochemical measurements. The intramolecular SH⋯OC and NH⋯S hydrogen bonds contribute to the redox potentials of Fc and iron-porphyrin moieties.Figure optionsDownload full-size imageDownload as PowerPoint slide