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N-(acyl)-\(\textit{N}^\prime \)-(ferrocenylidene)hydrazines and their nickel(II) complexes: Syntheses, structures and physical properties

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Abstract

The Schiff bases N-(acyl)-\(N^{\prime }\)-(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 \(\text {Ni(OAc)}_{2} \cdot \hbox {4H}_{2}\hbox {O}\), the Schiff bases (1 and 2) and \(\hbox {NaOAc}\cdot \hbox {3H}_{2}\hbox {O}\) in 1:2:4 mole ratio in refluxing methanol afforded the diamagnetic iron(II)-nickel(II)-iron(II) species [\(\text {Ni(Fcah)}_{2}\)] (3) and [\(\text {Ni(Fcbh)}_{2}\)] (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 \(^{1}\hbox {H}\) NMR) and cyclic voltammetric measurements. Molecular structures of 2, 3 and 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 (\(\hbox {Fcah}^{-}\) in 3 and \(\hbox {Fcbh}^{-}\) in 4) act as five-membered chelate ring forming azomethine-N and amidate-O donors and assemble a square-planar \({ trans}\hbox {-N}_{2}\hbox {O}_{2}\) 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).

Graphical Abstract

N-(acetyl/benzoyl)-\(N^{\prime }\)-(ferrocenylidene)hydrazines (HFcah and HFcbh) and their diamagnetic nickel(II) complexes [\(\hbox {Ni(Fcah)}_{2}\)] and [\(\hbox {Ni(Fcbh)}_{2}\)], each containing a bent iron(II)-nickel(II)-iron(II) array, were synthesised and characterised by analytical, spectroscopic and electrochemical measurements. Molecular structures of HFcbh and the two trinuclear complexes have been confirmed by X-ray crystallography.

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Acknowledgements

G. N. Babu thanks the Council of Scientific and Industrial Research, New Delhi for a research fellowship (No. 09/414(1025)/2012-EMR-I). Financial assistance and instrumental facilities provided by the Department of Science and Technology, New Delhi through the FIST and the PURSE programs and by the University Grants Commission, New Delhi through the CAS and the UPE programs are gratefully acknowledged.

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  1. School of Chemistry, University of Hyderabad, Hyderabad, Telengana, 500 046, India

    G Narendra Babu & Samudranil Pal

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  1. G Narendra Babu
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Correspondence to Samudranil Pal.

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Dedicated to Professor K. C. Kumara Swamy on the occasion of his 60th birth anniversary.

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Babu, G.N., Pal, S. N-(acyl)-\(\textit{N}^\prime \)-(ferrocenylidene)hydrazines and their nickel(II) complexes: Syntheses, structures and physical properties. J Chem Sci 129, 1105–1113 (2017). https://doi.org/10.1007/s12039-017-1280-8

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