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Name: Stephanie Wang Student ID Number: 1060139 Partner: Alice Chu Section: Chem 317 AA Synthesis and Characterization of (6-C6H3Me3)Mo(CO)3 Introduction: Organometallic chemistry is an area of chemistry that combines the disciplines or organic and inorganic chemistry, and organometallic compounds are typically characterized by the presence of a metal bound to an organic group. In the recent decades, the area of Organometallic chemistry has gained much recognition because of the interesting science happening and the wide application of organometallic compounds. Many organometallic compounds have been further researched due to their catalytic abilities. One area where organometallic catalysts are commonly used is the area of polymerization. For example, the Ziegler-Natta polymerization uses an organometallic catalyst to synthesize 1-alkene or -olefin polymers.1 One kind of Ziegler-Natta catalyst is titanium based catalyst with in the presence of a co-catalyst.1 One example reaction is depicted below.

Figure 1: An example of a Ziegler-Natta polymerization Here a 1-alkene is being polymerized with Titanocene dichloride as the catalyst and AlEt3 as the co-catalyst. Another common organometallic catalyst is the Grubbs catalyst which is used for

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olefin metathesis. An olefin metathesis is a reaction in which the fragments of alkenes (olefins) are redistributed by the scission and reformation of the carbon-carbon double bond.2

Figure 2: Olefin metathesis reaction Some common types of Olefin metathesis reactions are Ring-opening metathesis (ROM) and Ring-opening metathesis polymerization (ROMP).2 The Grubbs catalysts are a series of transition metal carbene complexes. Grubbs developed his first generation catalyst in 1992, and this was a ruthenium catalyst that was used for olefin metathesis reactions.2

Figure 3: Grubbs first generation ruthenium catalyst Grubbs then discovered his second generation ruthenium catalyst that was also used to catalyzed olefin metathesis.2 The second generation ruthenium catalyst proved to have a higher activity in reactions and was air/moisture sensitive.2

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Figure 4: Grubsbs second generation ruthenium catalyst Within this experiment the structure of Molybdenum hexacarbonyl, Mo(CO)6, will be examined, and more specifically the electronics of the CO ligand will be explored.

Figure 5: Molybdenum hexacarbonyl, Mo(CO)6 The interaction between the molybdenum and CO is interesting and can be detected via IR spectroscopy. In the Mo(CO)6 complex, the CO acts as a Lewis base ( donor) by donating its electrons to the molybdenums empty d-orbitals. The CO also has an empty -antibonding orbital located on the carbon in the CO. This empty orbital is able to act as a Lewis acid ( acid) as it accepts a pair of electron from the bond of the molybdenum. This phen omena is known as -backbonding, and can be detected by IR and NMR spectroscopy, and also has interesting repercussions to the electronics of the molybdenum. Herein, the synthesis and characterization of the Arene Molybdenum Tricarbonyl complex, (6-C6H3Me3)Mo(CO)3, will be discussed. Results: The following synthesis was carried out:

In the first step the Mo(CO)6 and mesitylene were placed into a Schlenk flask. A condenser was then attached to the Schlenk flask and the condenser was connected to a mineral oil bubbler to

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allow the carbon monoxide gas to escape. Everything was flushed with a moderate flow of N 2 gas. The reaction then stirred at reflux for 30 minutes. During reflux a color change from white to pale yellow was seen. After 30 minutes, the Schlenk flask was then cooled to room temperature and hexane was added into the solution to precipitate out the ( 6C6H3Me3)Mo(CO)3. The product was characterized by IR (KBr) and NMR (CDCl3) spectroscopy. The results are reported in Table 1 and Table 2 respectively. Table 1: IR data for Mo(CO)6 and (6-C6H3Me3)Mo(CO)3 Compound Mo(CO)6 (6-C6H3Me3)Mo(CO)3 Stretches IR(KBr) : 1971.6 cm-1 (w, vCO) IR(KBr): 3444.7 cm-1 (w, vAr-H) , 1948.2 cm-1 (s, vCO), 1882.7 cm-1(s, vCO) , 1653.8 cm-1 (w, vc=c) , 1447.2 cm-1 (w, vc-=c) , 1383.5 cm-1 (w, vC-H)

Table 2: NMR data for Mesitylene and (6-C6H3Me3)Mo(CO)3 Compound Mesitylene (6-C6H3Me3)Mo(CO)3. Type 1 H NMR (200.0 MHz, CDCl3)
1

H NMR (200.0 MHz, CDCl3)

Peaks 6.8 (s, 1H, C-H aromatic), 2.3 (s, 3H, C-H methyl) 5.2(s, 1H, C-H aromatic), 2.3 (s, 3H, C-H methyl) 2.2 (s, 0.2 H, C-H methyl)

Discussion: IR and NMR spectroscopy was used to characterize the product, (6-C6H3Me3)Mo(CO)3. The -backbonding effect that was previously mentioned puts some electron density into a CO antibonding orbital, which then weakens the CO bond. This weakening of the bond can be seen in the IR as the IR band for CO will be lower than the frequency of the CO stretch for free carbon monoxide, which is normally at around 2143 cm-1. The Mo(CO)6 compound has a stretch

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at 1971.6 cm-1 which is characterized as the CO stretch. Furthermore, the (6C6H3Me3)Mo(CO)3 compound has a stretch at 1948.2 cm-1 and 1882.7 cm-1 which are both due to the CO stretch (Table 1). The reason why the CO frequency is at a lower frequency for the (6-C6H3Me3)Mo(CO)3 compound is because mesitylene is a poorer acid and a stronger base than CO ,which allows the molybdenum to be more electron rich. This causes the frequency for the CO bond to be shifted lower in the (6-C6H3Me3)Mo(CO)3 compound because the CO antibonding orbitals carry more electron density further weakening the bond. Furthermore, the appearance of two CO stretches in the IR spectrum for (6C6H3Me3)Mo(CO)3 is due to the symmetry about the molybdenum center. The symmetry about the molybdenum center between the starting material, Mo(CO)6, and the product ,(6C6H3Me3)Mo(CO)3, is different. Mo(CO)6 has an octahedral symmetry about the center, while (6-C6H3Me3)Mo(CO)3 has a three-fold symmetry about the center. The change in symmetry about the molybdenum center alters the number of CO stretches in the IR spectra. Due to quantum mechanics selection rules, only one CO stretch is seen in the Mo(CO)6 complex because of its octahedral structure, while two CO stretches are seen in the IR spectrum of the (6-C6H3Me3)Mo(CO)3. Continually the stretches at 3447.4, 1653.8, 1447.2, and 1383.5 cm-1 from the IR spectrum of the (6-C6H3Me3)Mo(CO)3 are indicative of the presence of the arene complex in the product. The NMR shows relatively pure formation of the (6-C6H3Me3)Mo(CO)3 product. The NMR for the mesitylene has two peaks that were noted. There is a singlet at 6.8 ppm and a singlet at 2.3 ppm. The singlet at 6.8 ppm is from the hydrogens attached to the carbon-carbon ring, while the singlet at 2.3 ppm is due to the methyl hydrogens. The 1:3 integrations is due to

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the ratio between 9 methyl hydrogens and 3 ring hydrogens. The singlet at 0.097 ppm is due to residual silicon grease. The NMR for the (6-C6H3Me3)Mo(CO)3 had a singlet at 6.8 ppm, 5.2 ppm, 2.3 ppm, and 2.2 ppm. The singlet at 5.2 ppm is from the protons attached to the ring, while the peaks at 2.3 ppm and 2.2 ppm are from the methyl carbons. The singlet at 2.2 ppm and 6.8 ppm seems to be indicative of unreacted mesitylene due to the low integration. The integration between the 5.2 ppm and 2.3 ppm peak is 1:3, which is due to the three ring protons and nine methyl protons. Furthermore, the upfield shift of the aromatic protons peak is due to the large electron density on the molybdenum, which effectively shields the aromatic portons. The shift of the methyl protons is not affected because they are more shielded from the metal. Percent yield was 42.9%. Conclusion: Arene molybdenum tricarbonyl (6-C6H3Me3)Mo(CO)3 was formed and characterized by IR and NMR spectroscopy. Experimental: General Considerations: The reaction was carried out in the fume hood using a well-vented Schlenk line. The CO gas that was produced by the reaction escaped via a mineral oil bubbler. All reagents were provided and the product was characterized by using IR (KBr pellet) and NMR (CDCl3) spectroscopy. Synthesis of (6-C6H3Me3)Mo(CO)3 : Mo(CO)6 (2.01 grams, .00761 mol) and mesitylene (10 ml, .072 mol) was placed into a 100-ml round bottom Schlenk flask with a stir bar. A condenser was attached to the Schlenk

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flask and a mineral oil bubble was connected to the top of the condenser. The condenser was not cooled with water to allow the mesitylene vapors to reflux. The side arm of the Schlenk flask was connected to the Schlenk line and then purged with a flow of N2 for approximately 6 minutes, after purging with N2 gas the side arm stopcock was closed. The Schlenk flask was placed into a sand bath and heated to reflux, and allowed to reflux at a moderate boil for about 30 minutes. After 30 minutes the Schlenk flask was taken off of the sand bath and allowed to cool to room temperature under nitrogen. As it cooled, the mesitylene vapors condensed into a white solid. After the solution had cooled to room temperature hexane (20 mL) was added to complete precipitation. A yellow solid precipitated out after the addition of hexane. The product was then isolated by suction filtration and rinsed with hexane (10 mL). The resulting yellow solid was then dried (.979 grams, .0033 mol, 42.9%). IR (KBr): 3444.7 cm-1 (w, vAr-H), 1948.2 cm-1 (s, vCO), 1882.7 cm-1(s, vCO) , 1653.8 cm-1 (w, vc=c) , 1447.2 cm-1 (w, vc-=c) , 1383.5 cm1

(w, vC-H) NMR: 5.2(s, 1H, C-H aromatic), 2.3 (s, 3H, C-H methyl) 2.2 (s, 0.2 H, C-H methyl)

Supplement Information: Clearly labeled spectra are attached.

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Kissin, Y; Studies in Surface Science and Catalysis, 2008, 173, 4-10 Astruc, D; New J. Chem., 2005, 29, 42-56