Determination and Characterization of New Palladium Complexes and Study of their Properties

Shahriar Ghammamy¹ and Sajjad Sedaghat²

¹Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
²Department of Chemistry, Faculty of Science, Islamic Azad University, Malard Branch, Malard, Iran

DOI : http://dx.doi.org/10.13005/msri/090207

ABSTRACT:

In the current study, two complexes prepared using ligands derived from hydrazine, tris [N (2, 4 di nitro phenyl) N’-(3-Nitro benzylidene) hydrazine[Pd(C₁₃H₁₀N₅O₄)]Cl₂ and tris [N(2, 4 di nitro phenyl) N’-(3-phenyl alylidene) hydrazine[Pd(C₁₅H₁₃N₄O₄)]Cl₂ using spectrometry techniques of UV-VIS and IR methods. In the current compounds, the way these ligands bonding with central metal investigated using IR method. Substitutions of C=N and C=O indicate that palladium being coordinated with ligands.

KEYWORDS: Heterocyclic compounds; Coordination chemistry; FT-IR and UV–Visible spectroscopy; Hydrazine

Copy the following to cite this article: Ghammamy S, Sedaghat S. Determination and Characterization of New Palladium Complexes and Study of their Properties. Mat.Sci.Res.India;9(2)

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Introduction

Nitrogen-containing ligands such as Schiff bases and their metal complexes played an important role in the development of coordination chemistry resulting in an enormous number of publications, ranging from pure synthetic work to physicochemical¹ and biochemically relevant studies of metal complexes^2-6 and found wide range of applications. The development of the field of bioinorganic chemistry has increased the interest in Schiff base complexes, since it has been recognized that many of these complexes may serve as models for biologically important species.^7-11 The remarkable biological activity of acid hydrazides R– CO–NH–NH2, a class of Schiff base, their corresponding aroylhydrazones,R– CO–NH–NCH–R2 and the dependence of their mode of chelation with transition metal ions present in the living system have been of significant interest. Schiff base metal complexes have been widely studied because they have industrial, antifungal, antibacterial, anticancer and herbicidal applications. Several Schiff base complexes have also been shown to inhibit tumor growth. The effect of the presence of various substituents in the phenyl rings of aromatic Schiff bases on their antimicrobial activity has been reported.Resulting in an enormous number of publications, 107 ranging from pure synthetic work to physicochemical and biochemically relevant studies of metal complexes and found wide range of applications.Pd represents one of the most interesting transition metals applied to organic synthesis. Because of the unique combination of various properties relevant for catalytic cycles, its compounds are the catalyst of choice for a variety of rather different reactions such as hydrogenation, oxidation, and C-C coupling reactions. An enormous number of new Pdcomplexes, organometallic compounds, and supported Pdcatalysts for C-C coupling reactions in particular of the Heck type have been reported in the last 10 years. The motivation was to demonstrate useful applications of the presented neworganic ligands or organometallic compounds in the majorityof papers. However, there were also an increasing number of papers regarding in situ transformations that Pd catalysts undergo before and during the catalytic cycle and focusing on the nature of the true catalytically active species.In this paper we synthesized two new complexes of palladium with hydrazine ligands and identification them with FTIR and UV-VIS instruments.

Material and Methods

All reagents were supplied by Merck and were used without further purification. Melting point was determined in an Electro thermal 9200. The FT-IR spectra were recorded in the range 400–4000 cm^-1 by KBr disk using a Bruker Tensor 27 M 420 FT-IR spectrophotometer. The UV–Vis spectra in CH3CN were recorded with a Camspec M 350 spectrophotometer.Elemental CHN analyses were performed using a Heraeus CHN-O-RAPID elemental analyzer.

Synthesis of [Pd(C₁₃H₁₀N₅O₄)]Cl₂

C₁₃H₁₀N₅O₆ (0.1g) was stirred in DMSO (20cc) at 90 0C for 15 min and then PdCl₂ (0.01g) were dissolved in solution. The mixture was stirred and for 2 h to give a clear solution. After cooling to room temperature, the resulting brown precipitate was filtered, washed with n-hexane (20 ml) and dried. Mp: 239 0C Yield: 75%. Anal. Calc. for [Pd(C₁₃H₁₀N₅O₄)]Cl₂: C, 32.68; H, 2.09; N, 14.66%. Found: C, 32.83; H, 2.27; N, 14.81%. FTIR (KBr pellet, cm-1): 1615 (s, C=N), 3279 (w, N-H); 1330, 1512 (s, NO2), 3099(w, C-H), 523 (m, Pd-N). UV– Vis, ëmax (nm)/å (M-1cm-1); 255 (176), 379 (128), 381 (298). (Figure 1, 2).

PdCl₂+ 3 C₁₃H₁₀N₅O₆ ’! [Pd(C₁₃H₁₀N₅O₄₎]Cl₂.

Synthesis of [Pd(C₁₅H₁₃N₄O₄)]Cl₂

C₁₅H₁₃N₄O₄ (0. 1g) was stirred in DMSO (20cc) at 90 0C for 15 min and then PdCl₂ (0.01g) were dissolved in solution. The mixture was stirred and for 2 h to give a clear solution. After cooling to room temperature, the resulting red precipitate was filtered, washed with n-hexane (20 ml) and dried. Mp: 251-253°C Yield: 79%. Anal. Calc. for [Pd(C₁₅H₁₃N₄O₄)]Cl₂: C, 44.88; H, 2.99; N, 12.89%. Found: C, 44.95; H, 3.20; N, 12.97%. FTIR (KBr pellet, cm^-1): 1620 (s, C=N), 3279 (w, N-H); 1336, 1504 (s, NO₂), 2925 (w, C-H), 516 (w, Pd-N), 1504 (s, C=C). UV–Vis, λmax (nm)/ε (M^-1cm^-1); 223 (110), 237 (98), 266 (76), 305 (82), 395 (234). (Figure 3, 4).

PdCl₂+ 3 C₁₅H₁₃N₄O₄ → [Pd(C₁₅H₁₃N₄O₄)]Cl₂

Results

Synthesis and stability

Pd (II) salt reacts with Schiff base ligands in solvent to afford complex. These complexes are stable at room temperature. These [Pd(C₁₃H₁₀N₅O₄)]Cl₂ and[Pd(C₁₅H₁₃N₄O₄)]Cl₂were obtained in relatively high yield, 75 and 79% respectively. In this study we have reported the synthesis of new complexes of hydrazine derivative.The structural characterizations of synthesized compounds were made by using the elemental analysis, IR and UV spectral techniques.In summary, the synthesis and characterization of complexes have been described.

Figure 1: FT-IR Spectra of [Pd(C₁₃H₁₀N₅O₄)]Cl₂ in KBr Disk

Click on image to enlarge

FT-IRand UV-Vis Spectroscopic Studies

The IR spectra of [Pd(C₁₃H₁₀N₅O₄₎]Cl₂ show characteristic bands due to ν(C=N), ν(N-H), ν(NO2), ν(C-H) and ν(Pd-N) in the region 1615 cm^-1, 3279 cm^-1, 1330 and 1512 cm^-1, 3099cm^-1 and 523 cm^-1 respectively. The strong band in the region 1615 cm^-1, 1330 cm^-1 and1512 cm^-1 in the IR spectra of the [Pd(C₁₃H₁₀N₅O₄)]Cl₂ are assigned to ν(C=N)and ν(NO₂). IR spectra of [Pd(C₁₅H₁₃N₄O₄)] Cl₂ show broad weak intensity bands in the region 3279 cm^-1due to N-H, 2925 cm^-1 due to C-H and 516 cm^-1 due to Pd-N. The formation of [Pd (C₁₃H₁₀N₅O₄)] Cl₂and [Pd(C₁₅H₁₃N₄O₄)] Cl₂were also confirmed by UV–vis spectra. The absorption spectra of [Pd(C₁₃H₁₀N₅O₄)]Cl₂ and [Pd(C₁₅H₁₃N₄O₄)]Cl₂were recorded as 5×10^-3 M CH₃CN solutions in the range 200–800 nm using a quartz cuvette of 1 cm path length. The spectrum of [Pd(C₁₃H₁₀N₅O₄)]Cl₂ in CH₃CN solutions is shown that absorption band observed at 255, 379 and 381 nm and the spectrum of [Pd(C₁₅H₁₃N₄O₄)]Cl₂in CH₃CN solutions is shown that absorption bands observed at 223, 237, 266, 305 and 395 nm.

Figure 2: UV/Vis spectrum of [Pd(C13H10N5O4)]Cl2(in acetonitrile, C= 5×10-3M)

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Figure 3: FT-IR spectra of [Pd(C15H13N4O4)]Cl2in KBr disk

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Figure 4: UV/Vis spectrum of [Pd(C15H13N4O4)]Cl2(in acetonitrile, C= 5×10-3M)

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Discussion

Heterocyclic compounds constitute about sixty-five percent of organic chemistry literature. From straight chain aliphatic to branched to cyclic to aromatic, attention is currently paid to heterocyclic moieties, which are essential to life.In this paper, a direct, simple and one-step method has been used to synthesize these compounds. The advantages of the method are; that there is no side product, the reaction is quite fast, there are mild conditions, and the accompanied color change that provides visual means for ascertaining the progress of the reaction. [Pd(C₁₃H₁₀N₅O₄)]Cl₂soluble in di chloromethan, dimethyl sulfoxide (DMSO) andacetonitrileand isinsoluble in chloroform, water, toluene, hexane and methanol.[Pd(C₁₅H₁₃N₄O₄)]Cl₂ soluble in di chloromethan, dimethyl sulfoxide (DMSO), chloroform and methanol and insoluble in water, hexane, cyclo hexane and ether.In summary, Pd (II) has had, and continues to have, far-reaching impacts on organic synthesis. The versatile nature of palladium, in conjunction with the mechanistic understanding and predictive models that have been elucidated, has permitted a wealth of exploration into the seemingly endless potential of this metal. The synthesis and characterization of complexes have been described. Two complexes of Pd (²I) were synthesized simply. [Pd(C₁₃H₁₀N₅O₄₎]Cl₂ and [Pd(C₁₅H₁₃N₄O₄)]Cl₂were prepared by the reaction of C₁₃H₁₀N₅O₆ and C₁₅H₁₃N₄O₄ with Pd(Cl)₂. Electronic and vibrational spectra of these new complexes were studied.

Acknowledgment

We gratefully acknowledge the financial support from the Research Council of Takestan Islamic Azad University and many technical supports that provided by Tarbiat Modarres University.

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