Chiral planar 1,2-disubstituted ferrocenes: synthesis, spectroscopy, electrochemical characterization and DFT calculations

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Ferrocene compounds are an important class of organometallic complexes that display countless applications in the most varied fields. Among them, chiral ferrocenes play a significant role in the fields of chemistry and stand out as valuable catalysts in asymmetric synthesis. This work describes the synthesis and characterization of four 1,2-disubstituted planar chiral ferrocenes named (2-(diphenylthiophosphino)-ferrocenyl)methanol ( 1 ), N -(2-(diphenylthiophosphino)ferrocenylmethyl)-benzylamine ( 2 ), N -(2-(diphenylthiophosphino)ferrocenylmethyl)- tert -butylamine ( 3 ) and N -(2-(diphenylthiophosphino)ferrocenylmethyl)-isopropylamine ( 4 ). The compounds were comprehensively characterized by X-ray diffraction (XRD), FT-IR, FT-Raman, UV-Vis, cyclic voltammetry (CV), and electronic circular dichroism (ECD), supported by Time-Dependent DFT (TD-DFT) calculations. Theoretical analyses, including Quantum Theory of Atoms in Molecules (QTAIM) and reduced density gradient (RDG) analysis were applied to investigate the stability of the solid-state phase. The experimental and theoretical results showed excellent agreement, enabling the assignment of vibrational and electronic transitions, the determination of the absolute configurations of the enantiopure compounds, and the evaluation of their chiroptical and electrochemical properties. Overall, the combined experimental and computational approach provides a comprehensive understanding of the structural, spectroscopic, chiroptical, and electrochemical properties of these planar chiral ferrocene derivatives.