Synthesis and characterization of iron (iii) complexes of some 2-hydroxy-4, 5-dimethylacetophenone substituted hydrazones

Introduction

Transition metal complexes of Schiff base ligands have vital and expanded role in the expansion of coordination chemistry in biological systems since the late 19 th century. A large number of Fe(III) complexes, with coordination numbers ranging from 3 to 8 are known. The most common among there is complexes with coordination number 6 have octahedral geometry and this may be measured as their characteristic coordination polyhedron. Iron is necessary for life and a highly utilized element for all living organisms. It is involved in a extensive variety of physiological processes. Collaboration of dioxygen with iron compounds leading to different iron "oxygen complexes" plays an significant role in the active sites of a large number of iron proteins/enzymes [1][2][3] . The chemistry of iron is dominated by the +2 and +3 oxidation states i.e. iron (II) and iron (III) complexes e.g. Fe 2+ and Fe 3+ complex ions with selected ligands, generally of an octahedral shape, a few tetrahedral iron complexes are mentioned too. The reactions of the aqueous ions iron (II) and iron (III) with ammonia, caustic soda and washing soda are described and explained as are complexes of iron (III) with the chloride ion and cyanide ion. Iron is that the most abundant element found within the surrounding nature and plays essential role for the survival of terrestrial organisms. Iron also participates in biochemical processes like ribonucleic reduction, photo synthesis, nitrogen reduction, oxygen transport, energy production, and oxygenation. Ligands are designed and functionalized in order to deliver tissue specificity for the declivity of metal toxicity and improvement of pharmacological properties. Several iron (III) complexes have been known as contrast agent for magnetic resonance imaging. Some Fe complexes have been known for catalytic, antitumor, hypoxic selective cyatotoxins, and antimicrobial activity [4][5][6][7] . Iron and its complexes both are known for its DNA harmful property [8][9] . The developments within the field of bioinorganic chemistry have improved the attention in hydrazone complexes, because it's been known that a lot of those complexes may act as lead for biologically significant species [10][11][12][13][14][15] .

Experimental

Preparation of Fe complex with (E)-2-(1-hydrazonoethyl)-4,5-dimethylphenol metal Complex or tris (2-((E)-1hydrazonoethyl)-4,5-dimethylphenoxy)iron

(E)-2-(1-hydrazonoethyl)-4,5-dimethylphenol were synthesized following published procedure [16] . The transition metal complex tris(2-((E)-1-hydrazonoethyl)-4,5-dimethylphenoxy)iron was prepared by dissolution of (E)-2-(1-hydrazonoethyl)-4,5dimethylphenol ligand (0.019M) in ethanol at hot condition, an ethanolic solution (0.006M) of the Ferrous Sulfate was added drop wise with constant stirring and refluxed for 3 hrs. The resulting reaction mixture was cooled to room temperature and maintains pH 7 to 8 by addition of the 0.10N sodium hydroxide. Thus color green precipitate was formed. The resultant product was filtered, repeatedly washed with ethanol and dried at 40°C to 45°C temperature. The compound was re-crystallized in ethanol for purification and improving description. Reaction scheme preparation of tris (2-((E)-1-hydrazonoethyl)-4, 5dimethylphenoxy) iron is given below Scheme 1.

International Journal of Advanced Chemistry Research

Scheme 1: Reaction scheme preparation of tris (2-((E)-1-hydrazonoethyl)-4,5-dimethyl phenoxy)iron.

Preparation of Fe complex with (E)-4,5-dimethyl-2-(1-(2phenylhydrazono)ethyl)phenol metal complex Or tris(4,5dimethyl-2-((E)-1-(2-phenylhydrazono)ethyl)phenoxy)iron:

(E)-4,5-dimethyl-2-(1-(2-phenylhydrazono)ethyl)phenol were synthesized following published procedure 17

,4-dinitrophenyl)hydrazono)ethyl)-4,5dimethylphenol were synthesized following published procedure [18] . The transition metal complex tris( 2-((E

Results and Discussion

The Fe-Metal complexes were analyzed by Infrared spectroscopy, Ultraviolet-visible spectroscopy, 1HNMR, Carbon-Hydrogen-Nitrogen-Sulphur elemental analyzer, Decomposition temperature/Melting point, Molar Conductance, Magnetic susceptibility and Iron content by Gravimetric technique. Decomposition temperature / Melting points were recorded using Veego Scientific Device (Model: VMP-AD) in open capillaries and were uncorrected. Some physical properties of Fe-Metal complexes are mentioned in Table 1.

Infrared analysis

The IR spectra of Fe-Metal complexes were recorded in the region of 4000-400 cm -1 using FTIR spectrometer of model Agilent Resolutions Pro by direct sampling method.

The IR spectral data along with the possible assignments of Fe-Metal complexes are provided in Table 2, followed by IR spectra performed by IR direct solid method, use of Agilent Resolutions Pro and IR spectrum are showed in Figure 1, 2, 3. (2-((E

UV analysis

The UV spectra of the Fe-Metal complexes in methanol were recorded on SPECORD 50 PLUS-233 H 1409C Spectro photo meter, using a quartz cell of 1 cm optical path where methanol was used as a blank. The UV spectrum is shown in Figure 4, 5, 6.

The spectra shows V (bands maximum in nm) are provided in Table 3. 4.

Magnetic susceptibility

The magnetic moment (μeff) values at room temperature for Fe (III) complexes complexes was in the range of 4.5 to 5.3 B.M. These values are expected for Octahedral geometry of Fe (III) complexes at room temperature and further supported by electronic spectral data is summarized in Table 5. The molar conductance values at room temperature were measured in Methanol (10 -3 M) on an Elico digital direct reading conductivity meter model CM-180 is summarized in Table 6.

1 H NMR

We tried all Fe-complex 1HNMR and observe the spectrum of the complex differs from that of the free ligand in the following aspects: 1. Resolution is very poor due to the low solubility of Fe-Metal complexes in DMSO. 2. The disappearance of the signal due to the imine group, is attributed to its involvement in coordinating the Iron ion [19] .

3. The spectrum displays a multiple signal at δ (6.58-7.63 ppm) assigned to aromatic ring protons.

The 1H NMR Spectra of metal complexes are shown in Figure 7, 8, 9.

Acknowledgement

AcknowledgementsThe authors thank Mr. Pravin Daule and Mr. Dhole Anil, PG Department of Chemistry, New Arts, Commerce and Science College Parner, University of Pune, Dr. Raj Badekar, Riva Industries Ambernath, Mumbai, Dr. Pradeep Swain, Aveum Biolabs Pvt. Ltd., Hyderabad and Department of chemistry and Institute of Science, Mumbai for their valuable guidance and providing necessary facilities.

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