REPORT PROBLEMS

Schiff bases, is named after Hugo Schiff, formed when any primary amine reacts with an

aldehyde or a ketone under specific conditions. Schiff base are typically formed by the

condensation of a primary amine and an aldehyde which involves the use of organic solvents

such as methanol, tetrahydrofuran (THF), and 1,2-dichloroethane (DCE). Microwave-assisted

preparation of a series of Schiff base without solvent has also been reported. Schiff bases

have been shown to exhibit a wide range of biological activities, including antifungal,

antibacterial, antimalarial, antiproliferative, anti-inflammatory, antiviral and antipyretic

properties. In this assignment, we want to discuss biological activities of Schiff bases in terms

of antibacterial activity. We want to find out which metal complexes is more effective as

antibacterial. Also, we want to explore which metal complexes synthesis will gives us more

yield.

However, there have been some problems in the antibacterial activity. The lack of effective

treatment is the main cause of this problem. Development of new antibacterial agents with

novel and more efficient mechanisms of action is definitely an urgent medical need. In this

paper that we observed, the synthesis and antimicrobial activity were derived from the

condensation of 5-chloro-salicylaldehyde Schiff base derivatives. These derivatives are most

active against at least one of the evaluated bacterial species. Therefore, in this assignment we

want to find out between Cu(II), Co(II) and Zn(II) metals, which metal complexes are most

effective in antibacterial function. Therefore, we can decide which metal complexes is the

best in terms of their synthesis and effectiveness of antibacterial function.

SCOPE PROBLEMS

As we know, medicate resistances against antibacterial operators may be an issue in

their utilization for medical reason. The issue can overcome by the planning of metal

complexes, employing a process of chelation with the coordination

of transition metal particles. Schiff bases have N particles as their essential components.

Schiff base subordinates containing donor atom can act as great chelating agents for

the transition of metal particles. Research appears that, Schiff bases and their metal

complexes have been broadly examine due to their import anti-parasitic, fungicidal-

bactericidal, and anticancer properties. An assortment of Schiff base complexes inferred from

salicylaldehyde were found to have colossal applications in different areas. For example,

within the display investigation, we have integrated an arrangement of binucleating Schiff

bases inferred from the condensation of 5-bromo-3-fluorosalicylaldehyde and different chain

lengths of fragrant diamines and their metal complexes. Beginning from this aldehyde one

can get ready a huge number of Schiff bases and their metal complexes and these compounds

may find interesting applications in medicine, material science and catalysis..

In this proposal, comes about of our considers on the synthesis, characterization of a

few binuclear transition metal complexes determined from the over aldehyde and their

antimicrobial activities are displayed. Schiff bases, an aldehyde- or ketone-like compounds in

which the carbonyl group is replaced by an imine or azomethine, are a few of the

foremost broadly used organic compounds. Undoubtedly, they are broadly

utilize for industrial purposes additionally exhibit a wide run of organic exercises, counting a

nti-urease action. Ureases, enzymes that catalyze urea hydrolysis,

have gotten significant consideration for their affect on living organisms’ wellbeing, since the

persistence of urease activity in human and animal cells can be the cause of some diseases

and pathogen infections. These investigations led to the conception that Schiff bases of 5-
chloro-salicylaldehyde would possess potential antimicrobial properties. In this paper, the

synthesis of some Schiff bases of 5-chloro-salicylaldehyde and their antimicrobial properties

were reported. The results of this study may be useful to researchers attempting to gain more

understanding of the antimicrobial activity of Schiff base compounds.

Cobalt, copper & zn complexes with triazole Schiff bases (bidentate)

Figure 1: Structure of Schiff base (bidentate)

The Schiff bases in Figure 1 were soluble in ethanol and methanol. All the metal complexes

are coloured, non-hygroscopic solids, stable in air, infusible at higher temperature, insoluble

in water and many common organic solvents but they are soluble in DMF and DMSO.

A band at 1605–1620 cm-1 in the spectra of Schiff bases had been assigned to the azomethine

group frequency m (N‚CH), which shifted towards the lower frequency (Singh et al., 2006)

by 15–20 cm-1 in the spectra of the complexes, indicating coordination through the nitrogen

atom. Further coordination of metal to azomethine nitrogen was confirmed by a new band

around 483–528 cm-1 due to v (M–N). The Schiff bases exhibited a weak broad band around

2700 cm-1 due to v (S–H) vibrations (Singh et al., 2006; Kulkarni et al., 2010). This band did
not appear in the spectra of the metal complexes indicating deprotonation and complexation

through sulphur. In the spectra of metal complexes bands that appeared at 732–750 cm-1 and

334–348 cm-1 were assigned to v (C–S) and m (M–S), respectively. The presence of

coordinated water molecules in the metal complexes was indicated by a broad trough band in

the region of 3200–3450 cm-1. A strong band in the region of 1722–1735 cm-1 had been

assigned to v (OOCCH3) in 1:1 metal complexes.

Figure 1 : Example of the structure metal complexes

The synthesised Schiff bases act as bidentate ligands and coordinated to the metal ion through

Nitrogen and Sulphur of the thiol group.

Complexes derived from an asymmetric bidentate Schiff-base ligand (2-

((allylimino)methyl)phenol) at ambient temperature

Figure 1 : Synthesis of ligand (bidentate)

In the FT-IR spectrum of the ligand, a sharp band appeared at 1627 cm -1, which indicates the

C=N vibrations of the imine group. In the FT-IR spectra of the Schiff base complexes this

band appeared at 1623, 1621 and 1625 cm-1 for Cobalt(III), Copper(II) and Zinc(II),

respectively. The spectrum of free ligand shows strong band in 1328 and 1475 cm -1, assigned

to the C—O and C—N stretching of the ligand. However, after complexation of C—O and C

—N group via oxygen and nitrogen to the metal ion, these bands were observed at the region

of 1322 and 1449 cm-1 for Cobalt(III), 1328 and 1472 cm -1 for Copper(II) and 1323 and 1433

cm-1 for Zinc(II) complex. In complexes, absence of the phenolic O—H vibration indicates

that ligand is deprotonated in complexes.

NMR SPECTRA OF ZINC

The diamagnetic Zinc(II) complex, ZnL2, was studied by 1H and 13C NMR experiments.
The 1H and 13C NMR were shown and it gave the expected simple spectrum, indicating the

integrity of the complexes. The signal for the imine proton in the zinc complex appears at

8.17 and this is shifted downfield with respect to the corresponding signal in the free ligand,

indicating that the metal-nitrogen bond is retained in solution. No signal corresponded to

hydroxyl protons at 11.1 ppm, suggested that the hydroxyl groups are fully deprotonated and

the oxygen is most likely coordinated to the metal ions.

The 13C NMR spectrum shows 10 signals for ZnL2 complex. The peak at 171.5 ppm,

assignable to the imine carbon atoms, confirms the presence of the Schiff base in the

complex. Single crystal X-ray diffraction studies reveal that this complex to be a dimer with

bridging salicylaldiminato ligands resulting in a distorted trigonal bipyramidal geometry

around each zinc centre. Difference in kind of product can be resulted by two reasons: kind of

metal ion [(Zn(NO3)2.6H2O or Zn(OAc)2.2H2O)] and reaction condition (reaction under

reflux or in room temperature).

Metal(II) Complexes of Tetradentate Schiff Base Ligand:

(4E)-4-[(2-{(E)-[1-(2,4Dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one

Figure 1 : Structure of tetradentate Schiff base ligand

M(CH3COOH)2⋅𝑛H2O + H2LL → M(LL) + 2CH3COOH + 𝑛H2O

M = Cu(II),Zn(II) (𝑛=2 ); M = Ni(II),Co(II) (𝑛=4 )

 Table 1 : FTIR spectral data of the Schiff base ligand [H2LL] and its metal complexes.

The infrared of the ligand shows characteristic bands at 3475cm−1 that could be indicating to

the phenolic hydroxyl group, and the characteristics absorption at 1612cm−1 and 1243,

1271cm−1 can be assigned to v (C=N) and v (C-O) respectively. The band at 3475cm−1 was

absent in the spectra of the complexes; this indicative of the deprotonation and involvement

of the phenolic hydroxyl group of the ligand in bond formation with the metal ions.

The broad band at ∼3400cm−1 in the spectra of the Schiff base metal complexes is attributed

to the v (OH) frequency of the coordinated H2O. The FTIR spectra data confirmed the

coordination of the imino nitrogen and phenolic oxygen atoms to the Zn, Cu, Ni, and Co ions.

M = Cu(II), Ni(II), Co(II), and Zn(II)

where n=1for Zn(II); n=2 for Cu(II) and Ni(II); n=3for Co(II)

Figure 2 : Proposed structure of metal complexes

The spectral data show that the synthesized ligand binds with metal ions in tetradentate

through nitrogen atom of the azomethine and oxygen atoms of hydroxyl group of the 2’,4’-
dihydroxyacetophenone beside the hydroxyl group of the carboxyl group of the

acetylacetone, respectively.

Metal (II) complexes of Tridentate Schiff Base Ligands

Zn(II) with (2-(-(3-(dimethylamino)propylimino)methyl)-4-bromo-phenol).

Figure 3: Proposed structure of metal complexes with tridentate Schiff base ligand

IR spectra of the complexes shows distinct bands due to the azomethine (C≡N) groups within

the range of 1615-1630 cm-1. There is strong evidence for the presence of ionic perchlorate as

there is strong band at 1085cm-1. Also, there is strong band at 2091 cm-1 in the IR spectrum

which indicates the presence of thiocyanate in the complexes. Imine (C¿N) stretching

vibration is found at 1647 cm-1 in the ligands. The bands are shifted to lower frequency in the

complexes. These shifts are cause to the reduction of double band characters of the C¿N

bonds, causes by the coordination of nitrogen atoms to the Zinc(II) center. Due to O-H

stretching vibration in the IR spectrum around 3300 cm-1, free ligands has been drastically

reduced due to the participation of phenoxo oxygen atoms in coordination resulting with

concomitant deprotonation of the ligands. Position of bands comparable to C-O stretching

vibrations in free ligand also shift towards lower frequency region in complexes due to

involvement of oxygen atoms in coordination.

Co(II) metal with tridentate ligand Schiff Bases

Figure 3: Structure of tridentate ligands

Figure 4: IR spectral data of ligands and their Co(II) complexes

The ligands showed a band in the range of 1620-1650 cm-1 which is because of v(C¿ O ¿

group of the chromone moiety. This band was shifted to lower wavenumber region 5-48 cm-1

in their corresponding Co(II) complexes, indicating the coordination of oxygen atom of

carbonyl group of the chromone moiety. (Dziewulska-Kuaczkowska, 2010). In the range of

1605-1555 cm-1 the stretching vibrations of azomethine group C¿N was observed in all the

ligands. This band was shifted to 30-40 cm-1 lower wavenumber region in their cobalt(II)

complexes, indicating the participation of nitrogen atom of azomethine group in coordination

to the metal ion (Rosu et al., 2010). In HL1 and HL3 a broad band appeared at 3241 and 3246

cm-1, respectively is assign to the v(O-H) group. The absence of this band in their Co(II)

complexes is due to the involvement of oxygen atom of (OH) group in coordination with the

metal ion (Singh et al., 2010). While in HL2 ligand, a strong band appeared at 1365 cm-1, is

due to the v(C-O) of carboxylic group. In the Co(II) complex, it was shifted by 14 cm-1,

indicating the coordination of the oxygen atom of carboxylic acid with the metal ion

(Padmaja et al., 2011). S-H stretching vibrations has no significant role since the band value

is very weak HL4. However, participation of the SH group in chelation is ascertained from the

shift of v(C-S) at 790 cm-1 in the ligand to lower frequencies by 40 cm-1 in the complex

(Soliman and Mohamed, 2004). By the appearance of non-ligand bands at 600-400 cm-1, the

coordination of nitrogen and oxygen atoms was supported due to the v(Co-N) and v(Co-O)

region respectively. Therefore, we can conclude that the Schiff base ligands acts as

monobasic tridentate ligands with ONO/ONS donor sites.

YEAR AUTHOR FINDINGS
2017 Singh, K., Kumar, Y., Puri, P., Metals used :

Sharma, C., & Aneja, K. R. Cobalt, nickel, copper and zinc

Schiff bases :

Triazole (bidentate)
2015 Khorshidifard, M., Amiri Metals used:

Rudbari, H., Kazemi-Delikani, Vanadium(IV), Cobalt(III), Copper(II) and Zinc(II) complexes

Z., Mirkhani, V., & Azadbakht, Schiff bases :

R. (2-((allylimino)methyl)phenol) (bidentate)
2019 Nazirkar, B., Mandewale, M., & Metals used :

Yamgar, R. Cu (II) and Zn (II) complexes

Ligand :

5-aminobenzofuran-2-carboxylate
2015 Salehi, M., Amoozadeh, A., Antibacterial activities of two new Schiff bases.

Salamatmanesh, A., Kubicki, From ligand :

M., Dutkiewicz, G., Samiee, S., isophthalaldehyde.

& Khaleghian, A.
2015 Ejidike, I. P., & Ajibade, P. A. Tetradentate Schiff Base Ligand:

(4E)-4-[(2-{(E)-[1-(2,4-

Dihydroxyphenyl)ethylidene]amino}ethyl)imino]pentan-2-one.
2015 Anik Bhattacharyya, Suresh Metals used :

Sen, Klaus Harms & Shouvik Zinc(II)

Chattopadhyay Schiff bases :

Tridentate and tetradentate

2016 P.Kavitha, M.Rama Chary, Metals used :

B.V.V.A. Singavarapu & Cobalt(II)

K.Laxma Reddy Schiff bases :

Tridentate
2018 Xiang Liu, Carolina Manzur, Metals used :
 Nestor Novoa, Salvador Nickel, Copper, Vanadium, Manganese, Cobalt, Ruthenium

Celedon, David Carillo & Jean- Schiff bases :

Rene Hamon Unsymmetrically-substituted tetradentate

2016 Temitope E.Olalekan, Adeniyi Metals used :

S. Ogunlaja, Bernardus Copper(II)

VanBrecht & Gareth M. Schiff bases :

Watkins Tridentate NOS

2015 Ahmed M. Abu-Dief & Ibrahim Antibacterial activities of Schiff base complexes

M.A. Mohamed From ligand :

2-thiophene carboxaldehyde and 2-aminobenzoic acid.