Molybdenum Arene Draft Report

Oscar Hover, Monica Hong, Austin Engstrom

Introduction
The reaction of a metal hexacarbonyl with an arene proceeds through the following
scheme.
Molybdenum hexacarbonyl + mesitylene → Mesitylene molybdenum tricarbonyl + carbon
monoxide
Mo(CO)6(s) + C9H12 (l) → Mo(CO)3C9H12 + 3CO(g)

+ → + 3CO

Tungsten hexacarbonyl + mesitylene → Mesitylene tungsten tricarbonyl + carbon monoxide

W(CO)6(s) + C9H12 (l) → W(CO)3C9H12 + 3CO(g)

+ → + 3CO
Molybdenum hexacarbonyl + para-xylene → p-xylene molybdenum tricarbonyl + carbon
monoxide
Mo(CO)6(s) + C8H10 (l) → Mo(CO)3C8H10 + 3CO(g)

+ → +3CO

In the structure of theses products, all six of the carbons in the arene are bonded to the
metal. Thinking of these bonds as three double bonds, the arene supplies six electrons,
completing the 18-electron shell. Tungsten was chosen as a metal comparable to molybdenum
because it belongs to the same group and therefore can contribute the same number of electrons
ass molybdenum.
The CO ligands are π electron acceptors. This decreases electron density around the
molybdenum, allowing backbonding into a CO antibonding orbital, which decreases the strength
of the CO bond. By replacing three of the CO ligands with an arene, the added electrons allow
for more backbonding, and the stretching frequency of the CO bonds decreases. Thus, measuring
the IR spectra of these compounds can show patterns in the character of the other ligands
accompanying the CO.
The NMR spectra can also give insight into the structures of the compounds, giving
evidence for the actual structure of products.
Results

Figure 1: 1H NMR of mesitylene molybdenum tricarbonyl product

Figure 2: 1H NMR of mesitylene tungsten tricarbonyl product (crystal)
Figure 3: 1H NMR of mesitylene tungsten tricarbonyl product (filtrate)
Figure 4: 1H NMR of p-xylene molybdenum tricarbonyl product
 160

140

120

Transmission (%)
100

80

60

40

20

0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm^-1)

Figure 5: IR Spectrum of molybdenum hexacarbonyl starting material

140

120

100

Transmission (%)
80

60

40

20

0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm^-1)

Figure 6: IR Spectrum of mesitylene molybdenum tricarbonyl product

 120

100

Transmission (%)
80

60

40

20

0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm^-1)

Figure 7: IR Spectrum of mesitylene tungsten tricarbonyl product

120

100

Transmission (%)
80

60

40

20

0
4000 3500 3000 2500 2000 1500 1000 500 0
Wavenumber (cm^-1)

Figure 8: IR Spectrum of p-xylene molybdenum tricarbonyl product

 Table 1: Tabulated data of significant peaks in the NMR and IR spectra

Material NMR peaks (ppm) IR peaks (cm-1)

Mesitylene 6.77 -
2.25

Molybdenum hexacarbonyl - 1880

Mesitylene molybdenum tricarbonyl 5.24 1843

2.27

Tungsten hexacarbonyl - 1910

Mesitylene tungsten tricarbonyl (crystal) 2.15 -

1.55

Mesitylene tungsten tricarbonyl (filtrate) 5.11 -

2.44

p-Xylene 7.01 -
2.25

p-Xylene molybdenum tricarbonyl 5.61 1836

2.20

Yield:
Mesitylene molybdenum tricarbonyl: 1.015 g (0.00384 mol) of starting material yielded
0.674 g (0.00225 mol) of product. 100 * 0.00225/0.00384 = 58.59%
Discussion
In the NMR spectrum of mesitylene, there is a peak at 6.77 ppm, as well as at 2.25 ppm,
which represent the aromatic and methyl hydrogens, respectively. However, in the product NMR
spectrum, the aromatic peak is shifted upfield to 5.24 ppm, while the methyl peak remains close
to the peak in mesitylene, at 2.27 ppm. This suggests that the bonds to the molybdenum
tricarbonyl affect the aromatic hydrogens more that they affect the methyl hydrogens.
The mesitylene tungsten tricarbonyl crystal NMR spectrum suggests that the product was
not actually present or abundant in the crystal. Instead, there is evidence that the mesitylene
tungsten tricarbonyl was in the filtrate instead, which showed NMR peaks that aligned with the
predictions. The aromatic peak of the mesitylene
In the xylene product, we see this effect as well, with the aromatic peak shifted from 7.01
ppm to 5.61 ppm. The integral ratio has also changed, reflecting the fact that there are more
aromatic hydrogens and fewer methyl hydrogens in the mesitylene than in the xylene.
In IR spectra, free CO generally has a stretching frequency of above 2100 cm-1.1
However, CO as a ligand experiences backbonding, so it makes sense that the absorbance peaks
are below 2000 cm-1. Furthermore, the peak of the starting material (1880 cm-1) is higher than
that of the product (1843 cm-1). This shows that the added electron donation from the mesitylene
allowed for more backbonding than three additional CO ligands did.
Literature offers that the expected peak for tungsten hexacarbonyl is around 1997 cm-1,
and the peak in the product was at 1910 cm-1.2 This is consistent with the pattern exhibited by the
mesitylene and molybdenum hexacarbonyl experiment, and that when mesitylene replaced three
of the carbonyls on molybdenum hexacarbonyl, the added effect of backbonding shifted the peak
to a lower wave number.
For the p-xylene product, the IR peak shifted to an even lower frequency than the
mesitylene molybdenum product, at 1836 cm-1. This is the opposite of the prediction. Because
there are more methyl groups (electron withdrawing) on the ring, the arene should have allowed
or less backbonding, leading to a higher wavenumber.

1
George E. Ewing and George C. Pimentel, "Infrared Spectrum of Solid Carbon Monoxide", J. Chem. Phys. 35,
925-930 (1961) https://doi.org/10.1063/1.1701239
2
Raymond K. Sheline. Journal of the American Chemical Society 1950 72 (12), 5761-5762 DOI:
10.1021/ja01168a517
Experimental
General Considerations: Although the starting material and product are stable in air at
room temperature, the material is prone to decomposition at the temperatures at which the reflux
step is performed. Therefore, the synthesis step of the reaction was performed on a Schlenk line.
The starting materials were purged of air using a steady flow of nitrogen.

Synthesis of mesitylene molybdenum tricarbonyl: 1.015 g of molybdenum

hexacarbonyl, 10 mL of decane, and 10 mL of mesitylene were purged of air under a stream of
nitrogen. The nitrogen stream was turned off as the molybdenum hexacarbonyl was stirred in the
solution until it dissolved, and the solution was boiled for 30 minutes under reflux. The system
vented through an additional mineral oil bubbler. After 30 minutes, the nitrogen flow was turned
back on, and the system was cooled to room temperature. Once it was cool, the heating system
was dismantled. 10 mL of hexane were added to the solution to precipitate the product.

Synthesis of mesitylene tungsten tricarbonyl: An identical procedure to the mesitylene

molybdenum tricarbonyl was followed, except that tungsten hexacarbonyl was used instead of
molybdenum hexacarbonyl, and 20 mL total of decane were added to aid with dissolution, in
addition to the 10 mL of mesitylene.

Synthesis of p-xylene molybdenum tricarbonyl: An identical procedure to the

synthesis of the mesitylene molybdenum tricarbonyl was again followed, but 40 mL of para-
xylene were added instead of 10 mL of mesitylene.

Isolation of solid: The solution and precipitate were filtered using vacuum filtration. The
solid was rinsed with 5 mL of hexane.

Characterization: The IR spectra of the starting material (molybdenum hexacarbonyl)

and the product were measured using and ATR attachment on an Thermo Scientific FT-IR
Spectrometer. The NMR spectrum of the product (dissolved in CDCl3) and dilute mesitylene (in
CDCl3) were measured on a Bruker DRX-200 nuclear magnetic resonance spectrometer.