In the search of new organometallic precursors, this contribution describes a convenient synthesis to obtain new ferrocene-based sulfonyl diamine derivatives. The [(η⁵-C₅H₄SO₂NH-CH₂-CH₂-NH₂)Fe(η⁵-C₅H₅)] (1) and [(η⁵-C₅H₄SO₂NH-C₆H₄-NH₂)Fe(η⁵-C₅H₅)] (2) compounds were prepared by the reaction between (η⁵-C₅H₄SO₂Cl)Fe(η⁵-C₅H₅) and the respective diamine precursor: ethylenediamine (1) or p-phenylenediamine (2) in good yields (86% for 1; 70% for 2). Both compounds were characterized by conventional spectroscopic techniques (infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry and elemental analysis) and cyclic voltammetry. In addition, the molecular structure of 1 was determined by single-crystal X-ray diffraction.

A family of heterobinuclear ruthenium(II)-cobaloxime complexes of general formula [Ru(bpy) ₂ (5py-bpy)Co(XgH) ₂ Cl] ²⁺ , where XgH represents dimethylglyoximato (dmgH), methylphenylglyoximato (mpgH), or diphenylglyoximato (dpgH), was prepared and investigated for electrocatalytic reductive dehalogenation of organohalides. The Ru–containing axial metalloligand remained constant, while the substituents of the equatorial glyoximato ligands were systematically varied. Cyclic voltammetry revealed cathodic waves assigned to the Co(II)/Co(I) process at −1.49, −1.30, and −1.18 V vs Fc/Fc ⁺ for Ru–Co(dmgH), Ru–Co(mpgH), and Ru–Co(dpgH), respectively. Addition of hexachloroethane (HCA) or trans-1,2-dibromocyclohexane (1,2-DBCH) produced concentration-dependent cathodic current enhancements consistent with reaction of electrogenerated Co(I) with the organohalides. Foot-of-the-wave analysis provided apparent bimolecular catalytic rate constants, with Ru–Co(dmgH) exhibiting the highest values: (3.00 ± 0.55) × 10 ⁵ M ⁻¹ s ⁻¹ for HCA and (3.48 ± 0.06) × 10 ⁵ M ⁻¹ s ⁻¹ for 1,2-DBCH. Despite having the most negative Co(II)/Co(I) potential, Ru–Co(dmgH) showed the highest apparent catalytic activity toward both substrates, while the phenyl-substituted derivatives were markedly less active toward 1,2-DBCH. Comparison with mononuclear cobaloximes indicates that the Ru–containing metalloligand does not uniformly enhance activity, and that dehalogenation reflects a balance among Co(I) accessibility, reduced-state reactivity, and substrate accessibility.