G NARENDRA BABU
Articles written in Journal of Chemical Sciences
Volume 129 Issue 8 August 2017 pp 1105-1113 REGULAR ARTICLE
The Schiff bases N-(acyl)-N’-(ferrocenylidene)hydrazines (HFcah (1) and HFcbh (2), where acyl = acetyl in 1 and benzoyl in 2 and H represents the dissociable amide proton) were synthesized in high yields (74 and 81%) by condensation reactions of equimolar amounts of ferrocene-carboxaldehyde and the corresponding acylhydrazines in presence of acetic acid in refluxing methanol.Reactions of Ni(OAc) ₂·4H ₂O, the Schiff bases (1 and 2) and NaOAc ·3H ₂O in 1:2:4 mole ratio in refluxing methanol afforded the diamagnetic iron(II)-nickel(II)- iron(II) species [Ni(Fcah) ₂] (3) and [Ni(Fcbh) ₂] (4) in 60 and 68% yields, respectively. Both Schiff bases and the two trinuclear complexes were characterized by elemental (CHN) analysis, mass spectrometric, various spectroscopic (IR, UV-Vis and 1H NMR) and cyclic voltammetric measurements. Molecular structures of 2, 3and 4 were determined by single crystal X-ray diffraction studies. The cyclopentadienide rings in the ferrocene moieties are essentially in eclipsed conformation in all three structures. Deprotonated Schiff base ligands in each complex (Fcah− in 3 and Fcbh− in 4) act as five-membered chelate ring forming azomethine-N and amidate-O donors and assemble a square-planar trans-N ₂O ₂ coordination environment around the nickel centre. The redox active 1–4 exhibit an iron centred redox couple in the potential range 0.23–0.50 V (vs. Ag/AgCl).
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