Synthesis, Characterization and Photo Degradation Studies of New Mixed Ligand Transition Metal Complexes of Mefenamic Acid and Glutamine

 

Zeyad Safauldeen Abdullahe, Bayader F. Abbas, Athraa Salman ahmed, Lubna F. Mohammed, Hanan Kd. Shaaban, Wessal M. Khamis*

Mustansiriyah University, College of Science, Chemistry Department.

 

ABSTRACT:

Dentate ligands 2-[(2,3-dimethylphenyl)amino]benzoic acid (Mefenamic acid ) and 2,5-diamino-5-oxopentanoic acid(glutamine) were used as bidentate Lewis base to prepare solid complexes with Molybdenum (V), Tungsten  (V)) and Lanthanum(III). The Photo degradation study was achieved for the complexes solutions in methanol. The prepared complexes were characterized by using spectroscopy methods like FTIR, UV-visible, Melting points and flame atomic absorption spectroscopy were calculated for all complexes. Furthermore the molar conductance of 0.001 M solutions in acetonitrile and magnetic susceptibility were performed to elucidate the proposed geometry and structures of prepared complexes. Magnetic susceptibility displayed that complexes had not diamagnetic properties. Photo kinetic study was done for La and Mo Complexes to study the photo sensitivity of prepared complexes. Half time of the complexes` photo reaction were achieved and order of reactions were calculated which appear that photo reaction of La^III complex was from the first order and constant of reaction was calculated (1.62x10^-2) min^-1 and half time of reaction was (62.112) min. Also, order reaction of Mo (III) complex was from first order too, the value of constant of reaction was (1.88 min^-1) and half time of reaction was (26.6) min. TGA analysis of Mo^III was done.

 

 

 

INTRODUCTION:

Mefenamic acid: is a type of medicine of scientific name is [(2,3-dimethyl diphenyl) amino-2-carboxylic acid]. It is used in the treatment of many diseases, including muscular aches and pains, dental pain. New studies have revealed that beside to arthritis and pain, the relief of short-term moderate pain, cancer and neurodegenerative diseases like Alzheimer’s disease. Etc [1,2]. It is considered one of the best ligands to contain effective aggregates that are correlated with metal elements as the carboxylate group and the amine group that evolved an electron that can be given to a transitional element. The complexity of these drugs has opened the way for the prepared of more advanced thrombotic compounds with higher toxicity and effect than the original drug [3-5].

 

The complexity of this acid with Co in aqueous medium and study the characteristics of complex in terms of ambient conditions of temperature and acidity, was found to be very stable. According to the results acquired, mefenamic acid can be considered a suitable chelating agent for Co (II) that supply best or various pharmacological profiles than that of the free drug [6-7]. Glutamine: Amino acid are the unit building of proteins and the residues, first one is carboxylic acid group and the second amino acid group on the carbon. The more important amino acids are 20 which used to produce polymer in the body. These amino acids are the more important standard amino acids/The carboxylic (-COOH) and amino groups are ionized at fluid body to give zwitterion [8,9]. There are many scientists interested with the amino acid inorganic chemistry. Many complexes of glutamine were prepared. Laila and etal prepared complexes of Cu(II), Co(II), Ni(II) and Fe(II) complexes with glutamine as primary with imidazole derivatives as secondary ligand which were used as antibacterial compounds [10]. Glutamine from Coordination compounds displays different characteristic properties that count on the metal ion to which they are bound. The nature of the metal as well as The other type of Ligand in with the metal when the complex consists of mixed ligands, etc. these metal complexes have found wide application in diversified fields of human benefit. The amino acids have large importance among the chemicals since they are of the living systems. Besides, they find enforcement in many fields including industry, animal feed supplements, foods and pharmaceutical production [11]. Glutamine is the most many free amino acid in the human body, comprising 69% of the aggregate free amino acid grouping of muscle [12]. Thus, the present work stems from our interests to develop this chemistry further by synthesizing new ternary V(V), Mo(V), W(V), and La (III) complexes of a-amino acid L-glutamine and Mefenamic acid with N, N-donor heterocyclic bases. This amino acid with its terminal –C (=O)–NH₂ groupAnd studied these compounds in terms of thermal stability and photovoltaic. At this work, complexes of were prepared and characterized, photo study were determined to evaluate the sensitivity of prepared complexes to UV-visible light. Order of photo-reaction was gained by using the half time method and constant of this reaction was calculated for three different concentrations. 

 

EXPERIMENTAL:

Chemicals:

All Chemical materials and solvents were supplied by two companies Fluka and BHD.

 

Apparatus:

All measurements were done at Mustansiryah University laboratories and Baghdad University-College of Ibn Al-Haitham laboratories. Melting points were remarked in Coslab melting point apparatus. UV-Visible data was achieved by UV-1650R Shimadzu spectrophotometer, molar conductivity measurements using Philips conductivity meter. The amounts of metal in prepared complexes were gained, using Shimadzu model 6809 to score atomic absorption. The Infrared Fourier (FTIR) spectra were recorded by using FTIR 8300 Shimadzu spectrophotometer in the frequency range of (4000-500)cm^-1. The magnetic susceptibility of the prepared complexes was gotten by using Magnetic Susceptibility Balance Johnson Matthey.

 

Preparation of Metal Complexes:

A solution prepared of (1mmole) of 10ml hot ethanolic Metal chloride, 10ml of hot ethanolic of Mefenamic acid with (1mmole) and 10ml of hot ethanolic solution of (1mmole) Amino acid (Glutamine). The three hot solutions were mixed with the ratio (1Mefenamic:1Metal Chloride:1Amino Acid) and refluxed for 2hrs. After reflux, the solution was cooled and filtered. The precipitate was washed with cold water, then cleaned with hot ethanol, dried and gathered [13].  Table (1) showed the physical properties of the prepared complexes.

 

Table (1) shows the physical properties of prepared complexes:

Comp. No	Color %	M. P.	Mwt	Yield%	Suggested structure
La	Off white	200	553	75%	O.h
Tn	Light green	300	590	80%	O.h
Mo	Grey	300d*<	496	90%	O.h

d*= decomposed

 

Photo - degradation study of Complexes (La, Mo):

To calculated order reaction we presumed that reaction was from (zero, first, second, third) order reaction and radiated four concentration of complexes (1×10^-4,0.5×10^-5,1×10^-5,1×10^-6) M at different time (0,10,20, 30, 40,50,60,70,80,90,100, 110, 120,130,140,150.) min [14]. At all-time radiation, the absorbance of complexes concentration was recorded. Then the constant of the four concentrations were calculated. The Graphic between time of radiation at x-excess and the logarithm of variation of complex concentration at y-excess was obtained to calculated the slope of this graph which referred to (-k) of the photodegrading reaction. The supposed order which it`s graphics gave equal value of constant at constant temperature (25̊C) and pressure, represented the order of the photo degradantion reaction. Half time of radiation reaction calculated by using the equation [15]. t_1/2 = 1 /2K

 

RESULTS AND DISCUSSION:

FTIR Spectra:

Proton of the carboxyl group was eliminated in L₁ and L₂ and the carboxylate group be with negative charge. This return to small size and high acidity of hydrogen atom compared to the large oxygen atom and its high solubility. This causes the unclarified frequency of the (O-H) group as shown in (fig.1 and 2) [16]. The spectrum of (NH⁺³) had broad frequency band compared to(N-H) in glutamine compound which was located in the area (3331cm^-1). The previous band due to overlap of asymmetric vibration spin of the two groups (NHandNH⁺³) for the amino acid. Another band appeared at the region (1566cm^-1) referred to overlap between the symmetric vibration spin of (NH)and (NH⁺³). The carboxylate ion (COO^-1) was appeared a strong band in the region (1602cm^-1) and weak peak which was located at the region (1400cm^-1). These bands returned to (COO^-1) asymmetric and symmetric respectively. Also a broad and intense peaks were appeared at regions (2941,2860cm^-1) returned to the stretch (C-H) aliph. Group [17,18]. The FTIR spectrum of acid ligand showed some characteristic stretching bonds at (3420,1620,1500, 1608 and 1159) cm^-1 assigned to N-H, C=O,C-N ,Ar-C=C,C-O. The NH band of acid at 3340cm^–1 exhibited a significant shift upon of the complexes. The bands of values νas(COO) and νs(COO)of the two ligands gave new data to be<200 cm^–1 in deference between the spectra of acid, glutamine and the complexes. These data were suggested bidentate bonding for the two ligands [19-20]. The new band in the range of 486–449cm^–1 in the spectra of products was assigned to(M–O)bond formation [20].The table (2) shows a frequency changing for the complexes.

 

Scheme 1: show complex Mo⁺⁵

 

Table-2: Major Infra-red bands (cm^-1) for ligands and metal complexes 

Comp. No	ν(N–H)	ν(C=O)	ν(COO)		Δν	ν(M–O)
			νas(COO)	νs(COO)
L1	3340	1730	1673	1422	251	------
L2	3331	1725	1630	1418	212	-----
Mo+5	3171	1685	1622	1487	137	491
W+5	3190	1685	1627	1483	144	483
La+3	3192	1685	1626	1485	141	489

 

 

Figure (1). FT-IR spectrum for complex L₂

 

 

Figure (2). FT-IR spectrum for complex Mo

 

UV-Visible Spectra:

Electronic spectra of ligands L₁, L₂ beside their complexes were recorded in ethanol and DMSO solutions. The acid and glutanime base ligand L₁, L₂ displayed a absorption aroud (247,266) nm region assigning to the p®p* transition that is unaffected in formation of complexes. The peaks around 324 and 337nm are assigned to n®π* transitions of (-C-N-,-C=C, C=O)groups and intra-ligand charge transfer. D¹[La(III), Mo(V), W(IV)] the ground atomic term is ²D and the octahedral ground state ²T₂g[21]. Magnetic properties of lanthanides are currently of great interest. Magnetic susceptibility for the complexes was recorded in the solid state at 298K using Faraday’s way as an important source of magnetism. The f-block elements of lanthanides have the f-block elements of lanthanides have particularity magnetic proper -ties resultant to the presence of many odd electrons in their valence orbitals. The magnetic properties of rare earth ions are well known and are hegemony by the internal nature of the f orbital different from the 3d orbitals of transition metal ions in a ligand field [22]. The 4f electrons are accountable for the strong magnetism display by the metals and compounds of the lanthanides. In the imperfect 4f subshell the magnetic effects of the different electrons don`t cancel out each other as they do in a completed subshell, this factor gives rise to the interesting magnetic behavior of these elements. At high temperatures, all the lanthanides except lutetium are paramagnetic (weakly magnetic) which frequently shows a strong anisotropy. The amount of magnetism in the internal transient element is directly dependent on the individual electrons in the casing. The highest number is7 and cancels the electrons if the envelope is saturated. This is shown in(La⁺³)where magnetism equals (0) [23].

 

Table 3: UV–Vis data of transition metal complexes of mefenamic acid and glutamine.

Comp.	Band position λmax(nm)	Wave number ʋ cm-1	Assignment	Geometry	µ B.M.
L1	324 247	30864 40485	n®π* π ®π*	---	-
L2	237 266	42194 37593	n®π* π ®π*	----	-
MO+5	580 370 290	17241 27027 34482	2B2®2E 2B2®2B2 LMCT	Octahedral	1.65.
W+5	593 393 289	16854 26799 34564	2B2®2E 2B2®2B2 LMCT	Octahedral	1.64
La+3	374 306	26738 32679	n®π* π ®π*	square-pyramidal	0

 

Magnetism and Spectra La

Ln	Ln+3	State	Unpaired e-	Color		meff/mB
La	4f0	1S0	0	Colorless	0	0

 

Photo–degradation study:

At this study, the kinetic study was achieved to determine constant of photo reaction for two prepared complexes for (La^III, Mo^III). The order of these reactions was gained and half time of photo degradation reactions was calculated too. Kinetic study of La^III and Mo^III were achieved by supposing that photo reaction was from the first, second, third or zero order. For that the law of any above order reaction was applied and graph between the time of radiation reaction at x-Axis as following:

 

Photo degradation study of La^III complex:

This study showed that the reaction was from the first order. At graphic calculation the constant (k) of photo reaction was (1.61×10^-2 min^-1) for (1×10^-4) M by determined the slope which referred to the value (-k). At the same time, the value of constant for the concertation (5×10^-5, 1×10^-5 ,1×10^-6) M were determined (1.62×10^-2, 1.61×10^-2, 1.60×10^-2)min^-1 respectively and for the all different concentration, value of (k) was equal at constant condition from pressure and temperature which it meant that this reaction was from the first order. To confirm this result the law of zero order and second order were achieved and it showed that constant was different for the four concentrations. This gave evidence and enhanced that the photo degradation reaction was from the first order [14]. Half time of the reaction was determined by using the equation (t_1/2  = 1/2k). The result showed that half time of photo degradation was (62.112) min [15]. When we assumed that photo reaction was from zero order and radiated different concentrations with different time, data and it`s result and graphics gave different value of constant reaction for the four radiated concentration of complexes under constant temperature and pressure. This gave evidence that this reaction was not from zero order. The same steps were achieved to prove that reaction was from second or third order and all its results and calculation proved that reaction was not second or third order. All these determination boosted that photo reaction was first order and the photo degradation reaction depended on concentration of La<sup>III</sup> complex. That can be due to trace amounts or weight of complex with the compared to amount of solvent. Beside that, it can be clarified that only complexes participate at reaction because of using of methanol as inert solvent which didn`t tend to react with La^III complex, Fig. (3), (4) shows the calculation of constant of photo reaction [14-15]. 

 

A.   Photo degradation study of Mo^III complex:

The same calculation of order reaction were achieved for Mo complex and gave that this reaction was pseudo first order because of a lot amount of solvent with the compered of weight of complex. Photoreaction constant was determined and equal to (0.0186, 0.0187, 0.0189, 0.0188) min^-1[14]. Constant values for four concentration of (Mo) complex were equal when law of first order was applied with the compared of laws for the other order. Half time of degradation was obtained for the reaction and it was (26.6) min [15]. Fig. (4),(5) showed the constant determination for the two complexes.

 

 

Fig. (3): Constant of photo reaction at 10^-4M, 5×10^-5, 1×10^-5M, 1×10^-6M of La^III complex

 

 

Fig. (4): Constant of photo reaction at 1x10^-4,0.5×10^-5, 1×10^-5 ,1×10^-6of Mo complex.

 

TGA analysis of Mo^III complex:

Thermogravimetric analyses (weight changes) were performed for complexes in the temperature range from (25 up to 600)°C using Argon gas at the heating rate of 10°C/min. The thermal behavior of Mo(V) complex figure revealed that the complex is stable up to 594°C and do not display any weight loss below this temperature. It is strong directory, which represent that the complex is devoid of lattice water as well coordinated water in the coordination sphere. The main mass loss recorded up to 513°C indicated losing of organic species and the formation of a thermally stable metal oxide [24-25], Fig.5 showed TGA/DTG spectrum of Mo(V) complex.

 

Table 4: TGA/ DTG information and Decomposition steps with the temperature range and weight loss for Mo complex in an argon atmosphere.

Comp. formula	Decompos-ition stage	Temp. range (°C)	Nature of transformation/inter mediate formed% Mass mg found(calc.)	Removes species	Weight loss found	Weight Loss (Calc)	Nature of DSC peak and temp(°C)
[MoL1L2Cl2]Cl	1 st 2 nd 3nd	150- 235 235 - 415 415 - 594	14.98 (14. 66) 27.13 (27.07) 11.39(10.68)	-Cl2 ,CH3 -Cl , C3H6NO, C2H5,-C3H3	2.25 3.46 1.06	2.19 3.461	273 Endo

 

Fig. (5): Showed TGA analysis of Mo^III complex.

 

ACKNOWLEDGEMENTS:

Thanks should be given to my University (Mustansiriyah University) for all helping submitted to achieve this work. Thanks to Dean of Science College and Head of Chemistry Department. Thanks to all how is helping to achieve this research.

 

CONFLICT OF INTEREST:

Authors declare that, there is no conflict of interest regarding the publication of this paper.

 

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Received on 16.07.2019           Modified on 11.12.2019

Accepted on 22.04.2020         © RJPT All right reserved