P: ISSN No. 0976-8602 RNI No.  UPENG/2012/42622 VOL.- XII , ISSUE- II April  - 2023
E: ISSN No. 2349-9443 Asian Resonance
Novel Synthesis, Spectral and Antimicrobial activity on Complexes of Transition Metal Mn(II) with heterocyclic Ligands
Paper Id :  17550   Submission Date :  07/04/2023   Acceptance Date :  20/04/2023   Publication Date :  25/04/2023
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Raja Ram
Assistant Professor
Chemistry Department
Dungar College, (M.G.S. University)
Bikaner,Rajasthan, India
Abstract This study brief the novel synthesis ( green approach), spectral and antibacterial investigations on the complexes of Manganese (II) with derivative of nitrogen base of DNA ligands. The complexes have been characterized on the basis of elemental analysis, infrared, electronic spectra and magnetic susceptibility studies. Antibacterial activities of these ligands and complexes have also been reported on S. aureus and E.coli microorganisms. The diffuse reflectance spectrums of the complexes show bands in the region around 17636 cm-1 to 26881cm-1, assignable to 6A1g→4T2g, 6A1g→4Eg, 4A1g (4G) transitions. These are also typical of tetrahedral environment around the Manganese. The magnetic moment (5.79-5.92 BM) of the complex indicates high tetrahedral environment. The green method of synthesis of complexes have found easily, appropriate and eco-friendly.
Keywords Microwave, Amide, Manganese (II), Antibacterial.
Introduction
Manganese has been widely used in aluminium alloys and key component of low-cost stainless steel formation. Manganese-di-oxide (MnO2) is used in dry cells and as a catalyst. Potassium permanganate is commonly used as a potent oxidiser and as a topical medicine (disinfectant). Manganese is essential to iron and steel production by virtue of its sulfur-fixing, deoxidizing alloying properties (1). Other compounds that find applications are manganese oxide go into fertilizers and ceramics and manganese carbonate is the starting material for making other manganese compounds.Manganese phosphate is used for rust and corrosion prevention on steel. MnO is a brown pigment and that can be used to make paint and is a component of natural brick. Manganese will be mostly replaced with lithium battery technology in manufacture of disposable battery, standard and alkaline cells (2-3).
Aim of study In this research paper transition metal complex of Mn(II) prepared by novel synthesis (green microwave bio reactor). This is the main application of green chchemistry. In this paper transition metal manganese use for preparation of some complexes of this metal with the pyrimidine derivative ligands. These complexes for prepared by conventional methods well as microwave method but microwave method is so better because yield is better and less time consumeable and determine anti microbial activity of this complexes by gram positive and gram negative bacteria like that S. Aurus and E. Coli. The electronic spectral assignments are characteristic to the geometries adopted by metal ion in ligand environments. Thus, Mn(II) adopts tetrahedral geometry in the complexes of amide ligands.
Review of Literature

Manganese particles usually settle to earth within few days. Humans promote manganese concentrations in the anvironment by industrial activities and through kindled fossil fuels. Manganese that derives from human sources can also enter surface water, ground water and sewage water. Through the application of manganese pesticides, manganese enters in soil (4-5). Manganese plays an important role for growth of plants. Deficiency of manganese ions causes disturbances in plant mechanism. Many weeds also included Mn, clotbur root, chamomile, dandelion, fennel seed, fenugreek, ginseng, hops, horsetail, lemongrass, parsley, peppermint, vine and raspberry (6). In mammalian cells, manganese causes DNA damages and chromosome aberrations. Large amount of manganese affect fertility in mammals and are toxic to the embryo and foetus (7-8). Manganese has showed to cross the blood brain barrier and a limited amount of Mn is also able to cross the placenta during in the pregnancy period, enabling it to reach a developing fetus (9-10). Manganese deficiency in the foetus may also causes malformation of the inner ear, ataxia and bone malformation. Lack of co-ordination head retraction, tremor, loss of righting reflexes, hyper irritability, faulty cartilage and bone matrix formation, heart problems and learning difficulties also occur (11). Metal or metalloid amide are compounds which contain one or more (–CONH2) ligand groups or a simple derivative [such as –CONHR, -CONR2, where R = - CH3, -C6H5, - COCH3 etc.) attached to Mn(II) metal. (12-18). Abdi A et al have been synthesis and characterization New complexes of manganese (II) and copper (II) derived from the two new furopyran-3, 4-dione ligands: Synthesis, spectral characterization, ESR, DFT studies and evaluation of antimicrobial activity (19). Khali AM Eman et al have been discribe Preparation, spectroscopic characterization and antitumor-antimicrobial studies of some Schiff base transition and inner transition mixed ligand complexes. (20).

Methodology
For the synthesis of Mn(II) complexes with amide group containing ligands, a solution of Manganese Chloride (0.001 mole in 30 mL ethyl alcohol) has been taken in a 250 ml round bottom flask, in this solution respective amide ligand (i.e. N2PB, N2PA, N46DM2PB, N46DM2PA) (0.003 mole) was added slowly with constant stirring. The reaction mixture was placed on a magnetic stirrer with constant stirring for 6-7 hours at room temperature. In the microwave synthesis, the reaction mixture was irradiated in a microwave reactor at 600 W for 2-5 minutes. The solid precipitate obtained in both the methods was separated and crystallized. Crystals were purified and recrystalized with ethyl alcohol and dried under vacuum.
Result and Discussion

The complexes of Mn (II) with all the amide group containing ligands are stable at room temperatures over a long period of time. The manganese complexes under investigations were white (brown) coloured powder; these complexes were, partially soluble in DMSO and insoluble in all other solvents. The elemental and metal estimations give satisfactory results. The physical and analytical data of complexes are given in Table 1.


Vibrational Spectra

Vibrational   spectra   were   recorded   in   KBr   pellets   and polyethylene film in mid and far IR regions and some diagnostic bands are presented in Table 2.




1.   [Mn-(N2PB)2]Cl2

2.   [Mn-(N2PA)2]Cl2

3.  [Mn-(N46DM2PB)2]Cl2

4.  [Mn-(N46DM2PA)2]Cl2

Figures 1-4: Vibrational Spectra of Mn(II) Complexes

Magnetic Susceptibility Measurements

Complexes of bivalent manganese are known in both high spin (S=5/2) and low spin (S = 1/2) states. Because of the additional stability of the half filled d-orbitals manganese (II) generally forms high spin complexes which have an orbitally degenerate 6S ground state term and the spin only magnetic moment of 5.9 ± 0.1 BM is expected which will be independent of the temperature and of stereochemistry (22).

The magnetic susceptibility measurements have been carried out in the polycrystalline state at room temperature and the results are given in Table 2. All the manganese (II) complexes have magnetic moment values in the range 5.70-5.92 BM indicating the presence of five unpaired electrons and hence these are high spin complexes with tetrahedral coordinate manganese (23).

Electronic Spectra

The electronic spectra of the manganese complexes with amide group containing ligands show weak absorption in the visible region. This is presented in Table 3 and in Fig. 5 to 8.

The observed spectra of the manganese (II) complexes with the   ligands exhibit bands in the region 17636 cm-1 and 28011 cm-1 assignable to

6A1g ®4T2g and 6A1g ®4Eg, ® 4A1g (4G), transitions.

The electronic spectral transitions of manganese complexes with the ligands are typical of tetrahedral environment around the manganese (24).



5. [Mn-(N2PB)2]Cl2

6.      [Mn-(N2PA)2]Cl2

7.   [Mn-(N46DM2PB)2]Cl2

8. [Mn-(N46DM2PA)2]Cl2

Figures 5-8: Transition Spectra of Mn(II) Complexes

Thermal Studies

The complexes of Mn (II) with the amide group containing ligands show first order kinetics in their thermal decomposition reaction. This is based on a straight line plot of Coats and Redfern (for n = 1). Activation energy (Ea) has been calculated by the linearization method of Goats and Redfern. The   thermal studies give the description about the thermal stability of the complexes. It has been observed that no decomposition takes place at room temperature and complexes are fairly stable well above the room temperature. The initial decomposition started above 500K.

Antibacterial Activity

The antibacterial activity of the compounds against S. aureus and E.coliwere carried out using Muller Hinton Agar media (Hi media). The activity was carried out using paper disc method is represented in fig.13-14 which shows all the Mn(II) complexes have moderate antibacterial activities against these bacteria.


FIGURES 9-12: Tentative structure of complexes

Fig.13. Biological activities of amide Ligands.

Fig.14. Biological activity of metal complexes Containing amide Ligands.

Conclusion On the basis of IR spectra, the amide group containing ligands show bidentate behavior in Mn (II) complexes by coordinating through carbonyl oxygen of amide groups and nitrogen of pyrimidine ring. The electronic spectral assignments are characteristic to the geometries adopted by metal ion in ligand environments. Thus, Mn (II) adopts tetrahedral geometry in the complexes of amide ligands. The magnetic moments tally with the electronic spectral data. On the basis of these studies the tentative structures have been proposed for the complexes and which are given in Fig. 9 to 12 for Mn (II) complexes. The complexes synthesized by novel green method are at par with conventional synthesis and in many cases yield was found to be better than conventional synthesis.
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