Fall

13

Infrared spectrum of DMSO Complexes

Name: Nicole Lapeyrouse PID: 3373674

Abstract Dimethylsulfoxide (DMSO) is an ambidentate ligand, which means that it has two different sites in which an atom can bind to. The two sites that an atom can bind to on DMSO is either the sulfur or oxygen atom. Using infrared spectroscopy the site in which Palladium, Ruthenium, and Copper bind to on DMSO can be determined by the absorption of the S=O bond, which absorbs at 1050 cm-1. If the absorption frequency increases than the atom bonds to the sulfur atom and if the absorption decreases the atom binds to the oxygen atom. According to literature values binds to the -1 oxygen atom and absorbs around 960 and 910 cm , PdCl2 2 DMSO binds to the sulfur atom and absorbs around 1157-1116 cm-1, and RuCl3 4 DMSO binds to both the sulfur and oxygen atom and absorbs at about 1088 and 910 cm-1.i The results that were obtain for this experiment shows that absorbed at both 980 and 898, PdCl2 2 DMSO absorbs at 1113.59, and RuCl3 4 DMSO absorbs at 1084 and 930.

Introduction Infrared spectroscopy is a common spectroscopic technique and can be used to identify organic compounds, functional groups, the determination of molecular structures, and a variety of other general uses. The infrared region spans the spectrum in wavenumbers from 12,800 to 10 cm-1 and is divided into three regions near-IR, mid-IR, and far-IR. The absorption of infrared radiation depends on the molecular species and this causes a transition from one vibrational or rotational energy state to another.ii An ambidentate ligand has two different sites for which an atom can bind to. Some examples of ambidentate ligands are CN-, NO2-, and S2O32-.iii The site of binding for CN-is with either the lone pair on the C- atom or the lone pair on N- group (fig. 1). For NO2- atom the sites for binding could be the lone pair

1)

2)

3)

Figure 1: The following ambidentate ligand structures are as followed 1) CN-, 2) NO2-, and 3) S2O32-.ii

of electrons on N- or the lone pair of electrons on the O- atom (fig. 1). The S2O32- structure displays two sites for which an atom could bind to either the lone pair on the S- or the lone pair on the O- atom. In this experiment the infrared spectroscopy is being used to determine the site in which metals bind to DMSO. In DMSO the S=O bond absorbs at 1050 cm-1 in the infrared region, which this absorption can be used to identify which atom the metals binds to. If the metal binds to the sulfur atom then the absorption frequency will increase because the metal atom is donating electrons to the sulfur atom. However, if the metal binds to the oxygen atom the metal will form a bond with the lone pair from the oxygen and the absorption frequency will decrease.iii Procedures This experiment required the preparation of three separate compounds, which were copper(II) chloride, palladium(II) chloride, and ruthenium(III) chloride trihydrate. The preparation of was prepared into a 10 mL Erlenmeyer flask by dissolving 150 mg of CuCl2 in 1 mL of ethanol. Then into the Erlenmeyer flask 250 L of DMSO was slowly added, while the mixture was being stirred with a magnetic stir bar. Once the DMSO was added an immediate color change occurred resulting in a light green precipitate (Fig. 2). The precipitate was collect by using vacuum filtration and rinsing the product twice with 500 L of ethanol. Once the crystals were collect the product was dried in a desiccator.

Figure 2: CuCl2 precipitate

The preparation PdCl2 2 DMSO was prepared in a 10 mL Erlenmeyer flask. Into the flask 1.25 mL of DMSO was added with a magnetic stir bar. Then 135 mg of PdCl2 was slowly add into the flask and the solution was left to sit until it turns a dark brown (Fig.3), which takes about 2.5-3 hours. The product was left standing until an orange crystal was produced. Once the crystals were produced the use of vacuum filtration was used to collect the crystals it was rinsed twice with 500 L of ether. The crystals were left to dry.

Figure 3: PdCl2 2 DMSO precipitate

The preparation of RuCl2 4 DMSO required a simple reflux. Into a 10 mL round bottom flask 100mg of RuCl3 xH2O was weighed. The flask to the water condenser was attached and placed into a sand bath. The apparatus that was used is displayed in figure 4. Heat was applied for about 5 minutes until the solution changes color to orange. The solution was transferred into a 10 mL beaker and sat until crystals formed. Once the compound had formed crystals 2 mL of acetone was added dropwise until the formation of two layers formed. Then it was place in an ice bath for 10 minutes. After cooling for the allotted time the yellow crystals that had formed were collected by the use of vacuum filtration and the crystals were washed once with 500 L of acetone and then followed with 500 L of ether.

Figure 4: The apparatus used for the preparation of RuCl2 4 DMSO.

Once the compounds had dried the melting point or the decomposition point were determined. The samples were then analyzed by using an Infrared spectroscopy. Results Table 1: Results RuCl2 Mass (g) Molecular weight (g/mol) Theoretical Yield Actual Yield (%) Melting point ( C)
o

PdCl2 0.2425 177.31 0.3847 63.0442 214-216

0.3314 170.48 0.4457 74.3625 212-214

0.2554 207.43 0.5639 45.2934 158-162

Figure 5: IR spectrum of DMSO

Figure 7: IR spectrum of

Figure 8: The preparation of PdCl2 2 DMSO

Figure 6: IR spectrum of RuCl2 4 DMSO

Discussion DMSO is a dipolar aprotic solvent, which means that it does not contain O-H or N-H bonds and have a large dipole moment. The advantage to having a dipolar aprotic solvent is that it cannot hydrogen bonds with it self. Also the dissolution process of DMSO is an excellent solvent for polar compounds such as: acids, alkalis, metals, and cations because of the dipole moment. In comparison to water, which is a dipolar protic solvent, that can solvate polar solvents and anions readily because of the hydrogen bonding. This dipolar aprotic characteristic of DMSO is an important characteristic because it allows it to participate in having metals bind to it at different sites. DMSO is an ambidentate ligand and metals can bind to either the sulfur or to the oxygen atoms.iv The metals are able to bind to DMSO because it can act as both a hard and soft base, which this allows soft and hard acids to bind to it. Soft acids are defined generally as a Lewis acid, an electron pair acceptor, and their size is moderately large. The characteristics of hard acids are the opposite, which have a low polarization and have smaller sizes. If the metal binds to the sulfur atom then the metal is a soft acid and the absorption frequency will increase because the metal atom is donating electrons to the sulfur atom. However, if the metal binds to the oxygen atom the metal is a hard acid and the metal will form a bond with a lone pair from the oxygen. v The fundamental theoretical reasons behind the hard-soft acid base (HSAB) rules are due to the orbitals. The more closed shells that are prevalent around the nucleus the more shield it is. For the soft acids they have more shielding versus the hard acids where they have less shielding. In this experiment RuCl3, CuCl2, and PdCl2 were analyzed to determine the site of binding to DMSO by the use of the IR spectra. In the IR spectra it shows that absorbed at both 980 and 898, PdCl2 2 DMSO absorbs at 1113.59, and RuCl3 4 DMSO absorbs at 1084 and 930. According to literature values binds to the oxygen atom and absorbs around 960 and 910 cm-1, PdCl2 2 DMSO binds to the sulfur atom and absorbs around 1157-1116 cm-1, and RuCl3 4 DMSO binds to both the sulfur and oxygen atom and absorbs at about 1088 and 910 cm-1.vi The values obtain by the IR corresponds to the literature values. Based on where the atoms bind to DMSO (either the sulfur or the oxygen atom) determines whether they are a hard or soft acid. The PdCl2 atom binds to the sulfur atom indicating that it is a soft acid. As for CuCl2 it binds to the oxygen atom indicating that it

is a hard acid. However, the RuCl3 binds to both the oxygen and sulfur atom making it a borderline acid or base. Using the data that was collected and the general idea of the HSAB theory it is possible to predict the binding sites of Pt3+, Hg2+, Fe2+, and Zn2+ to DMSO. The predict sites of binding would be that Pt3+, Hg2+, and Zn2+ would be soft acids and bind to the sulfur atom while Fe2+ would bind to the oxygen indicating it as a hard acid. Reference
i

Nakamoto, Kazuo. Infrared and Raman Spectra of Inorganic and Coordination Compounds. New York: Wiley, 1986. Print. ii Skoog, Douglas A., F. James. Holler, and Stanley R. Crouch. Instrumental Analysis. iii Prakash, Satya. Advanced Inorganic Chemistry. New Delhi: S. Chand &, 2005. Print. iv Metal complexes of DMSO and FT-IR spectroscopy Linkage isomerism v Pike, Ronald M., and Mono M. Singh. "Metal Complexes of Dimethyl Sulfoxide." Microscale Inorganic Chemistry: A Comprehensive Laboratory Experience . By Zvi Szafran. N.p.: n.p., n.d. 218-22. Print. vi Nakamoto, Kazuo. Infrared and Raman Spectra of Inorganic and Coordination Compounds. New York: Wiley, 1986. Print.