Kenta Sueyoshi

1262997

CHEM 317 AA
Arene Molybdenum

6/10/15

Introduction:

Organometallic complexes are metal centers with organic ligands attached to

them. They are very important in the field of chemistry because of their use as catalysts
to form important molecules in the industrial plant like acetic acid and polyethylene.

Ligands in this experiment, mesitylene and carbonyls, act more like a covalent bond than
a Lewis base due to the back bonding of the carbonyls to the metal center. Besides

donating two electrons, the carbonyl has an empty pi orbital, making it possible for the
molybdenum center donate electrons back into the carbonyl, which is called back

bonding. By have a back bond, the metal center can have low oxidation states like the

molybdenum, which has an oxidation state of 0 in Mo(CO)6. To keep the 18electrons,

when Mo(CO)6 is reacted with mesitylene, three carbonyl ligands come off so that the

mesitylene can bond to the molybdenum center, similar to a chelating tris-alkene ligand
(Figure 1). The synthesis is carried out to observe this arene bonding and its effects on

the structure of the metal center. This product can be characterized with IR and 1H NMR
spectroscopy. With IR spectroscopy, the symmetry of the starting material is octahedral,

so only one carbonyl peak is found. However, once the reaction occurs, the symmetry of

the molybdenum center becomes C3V symmetrical, so two carbonyl peaks would show up
in the IR spectrum. In the case of 1H NMR, two peaks with a 1:3 ratio should be seen,

indicating the mesitylene protons. Although the mesitylene is bonded to molybdenum in

the product, the proton NMR peaks do not shift very much due to its symmetry (Price
1967). Along with mesitylene, molybdenum hexacarbonyl was reacted with

cycloheptatriene and hexamethylbenzene to observe its effects on the back bonding of the
carbonyls. If the metal center becomes more electron rich, the metal can donate more
electron density to the carbonyls, creating a stronger back bond, and causing the IR
carbonyl peaks to shift upfield, and vice versa. Compared to mesitylene,

hexamethylbenzene has three additional weak electron donating groups, so the IR peaks

should go up in energy, whereas cycloheptatriene is not aromatic, so the IR peaks should

shift down in energy.

Figure 1: The reaction of interest between molybdenum hexacarbonyl and mesitylene to form mestitylene molybdenum
tricarbonyl is shown above

Figure 2: The same reaction as with mesitylene, but with cycloheptatriene

OC
OC

CO
Mo
CO

CO
CO

OC

Mo
CO

CO

Figure 3: The same reaction as with mesitylene, but with hexamethylbenzene

Experimental:
(6-mesitylene) molybdenum tricarbonyl, (6-C6H3Me3)Mo(CO)3
The procedure from Angelici was followed, but half the amounts of reactants

were used (1968). Mo(CO)6 (1.063g, 0.0038mol) and mesitylene (5mL) were heated and
stirred under reflux in an inert atmosphere of nitrogen for half an hour. After reflux, a

flow of nitrogen using a Schlenk Line was used to condense unreacted mesitylene and

remove unreacted Mo(CO)6, and the reaction mixture is cooled to room temperature. A

yellow solution was expected, but a black solution was formed. So instead of adding

hexane to complete precipitation, a distillation column was used to separate the solution

and the black impurity. The solution remained a black color, but had a tint of yellow to it.
This solution was put on the rotary evaporator to collect a yellow-ish black precipitate of

4.66% yield (0.053g, 0.00018mol). 1H NMR (CDCl3) 2.266 and 5.239 ppm. IR (Nujol)
CO 1899.6 and 1986.9 cm-1.

(6-Cycloheptatriene) molybdenum tricarbonyl, ( 6-C7H8)Mo(CO)3

Mo(CO)6 (1.045g, 0.0038mol), cycloheptatriene (4.0mL, 0.038mol), and 10mL of

decane were heated and stirred to reflux for two hours under inert atmosphere using the
Schlenk Line. A flow of nitrogen was used to cool the solution to room temperature,

filtered through neutral alumina, washed with 30mL of ligroin and CH 2Cl2. The product
was put on a rotary evaporator, and then put under vacuum to completely dry the

precipitate. A 27.95% yield (0.289g, 0.001mol) was obtained from this procedure.
1

H NMR (CDCl3) 2.537, 3.035, 3.644, 4.986, and 6.112 ppm. IR (Nujol) CO 1904.1,

1929.3, and 1994.0 cm-1.

(6-Hexamethylbenzene) molybdenum tricarbonyl, (6-C6Me6)Mo(CO)3

Mo(CO)6 (1.032g, 0.0038mol), hexamethylbenzene (0.615g, 0.0038mol), and

decane (20mL) were heated and stirred to reflux for two and a half hours under inert

atmosphere using the Schlenk Line. A flow of nitrogen was used to cool the solution to
room temperature, and then the product was washed and filtered using pentane. A

11.77% yield (0.153g, 0.00045mol) was obtained from this procedure. 1H NMR (CDCl3)
2.340ppm. IR (CH2Cl2 Thin Film) CO 1937.1 and 1965.4 cm-1.

Results/Discussion:
These IR results are what were expected. Since in the starting product, Mo(CO) 6,

the symmetry of the complex is octahedral, and all of the carbonyls are equivalent, only
one peak will appear in the IR spectrometer. Once the molybdenum reacts with

mesitylene, the symmetry of the complex becomes C 3V, so two different peaks for the

carbonyls appear. This is observable in the IR spectrum with the one peak in Mo(CO) 6 at
1986.7cm-1. This one peak become two peaks in (C6H3Me3)Mo(CO)3 at 1986.9cm-1 and
1899.6cm-1. Based on this information, the final compounds, mesitylene molybdenum

tricarbonyl was successfully synthesized. However, other than the carbonyl peaks and the
nujol peaks, no peaks representing the mesitylene was observable. This is odd, because

the change in symmetry of the molybdenum complex is observed through the two peaks

of carbonyl, and this change is caused by the addition of the mesitylene ligand. A source
of this error is most likely due to the low concentration of the product in nujol when
taking the IR.

When the ligand on molybdenum became hexamethylbenzene, the symmetry of

the complex stayed the same as the mesitylene complex, so two carbonyl peaks at 1937.1
and 1965.4cm-1 were observed. As expected, the carbonyl peaks of split into two peaks
because of the change of symmetry, suggesting the successful synthesis of

hexamethylbenzene molybdenum tricarbonyl. However, compared to the mesitylene

complex, the two peaks did not shift up in energy. While one peak rose in energy, the

other peak decreased in energy. This could have occurred due to the methyl groups on the

benzene rings. In the case of hexamethylbenzene, there are six methyl groups, making the
carbonyl groups always eclipsed to methyl groups. On the other hand, in mesitylene,

there are only three methyl groups, so the carbonyls can either be eclipsed or staggered.

The ability to have these two conformations may have caused the larger gaps between the
peaks compared to hexamethylbenzene.

The symmetry of the metal complex is lost when cycloheptatriene is added as a

ligand, causing three distinct carbonyl peaks to appear at 1904.1, 1929.3, and 1994.0cm -1.
These three peaks support the synthesis of cycloheptatriene molybdenum tricarbonyl, but
unexpectedly have higher energies. Since cycloheptatriene is not aromatic, it was

expected that the loss of electron density would weaken the back bonding of the

carbonyls, allowing them to vibrate at a lower energy. The increase in energy of the

carbonyl peaks may have resulted from the delocalization of electrons with in the ring.
Since cycloheptatriene does not have any substituents on the ring, the delocalized
electrons stay in the ring, allowing more electron donation to the metal.

The 1H NMR came out to be what was expected with two singlet peaks. The first

peak at 2.266ppm represents the protons on the methyl groups of the arene ring, while the
peak at 5.239ppm represents the protons directly on the arene ring. Although integration
values of 3:1 were expected, 5:1 was found. This may have occurred because the

relaxation of the bonds, when measured, takes longer on the methyl groups, causing them
to show a larger integration peak than what is expected. Although the methyl group

chemical shifts are around 2.27ppm in both pure mesitylene and in the complex, the arene
protons shift from about 6.8ppm to 5.2ppm. This shows that when the molybdenum is
bonded to the arene ring, it must be donating electrons back into the ring, causing the
chemical shift to go upfield.

When hexamethylbenzene is the ligand, however, the chemical shifts move

slightly downfield compared to the pure material. The singlet peak at 2.340 for

hexamethylbenzene molybdenum tricarbonyl shows that the results are as expected, and
the synthesis was successful. The chemical shift of the product may have shifted
downfield compared to the pure material because hexamethylbenzene has more

substituents compared to mesitylene. By having more methyl groups on the ring, there

will be more electron density available and delocalized to the metal, causing a shift in the
peak.

Similar to mesitylene, when cycloheptatriene bonds to molybdenum, many of the

peaks shift up field. Comparing to literature values, the peaks at 2.537, 3.035, 3.644,

4.986, and 6.112ppm most likely represent the cycloheptatriene on the molybdenum,

supporting the synthesis of cycloheptatriene molybdenum tricarbonyl. The two peaks at

2.537 and 2.025ppm can be identified as the two protons on the non-double bonded

carbon in the ring because its integral values are close to half of the other peaks. These
two peaks most likely shifted downfield from 2.254ppm because of how the ring turns

into a boat-like structure when attached to the metal center. The other peaks most likely

shifted up field because the electrons are not delocalized, making the electrons readily
available to donate into the metal.

During the experiments, the successful synthesis of cycloheptatriene molybdenum

tricarbonyl and hexamethylbenzene molybdenum tricarbonyl was apparent due to its

bright red and yellow colors, respectively. However, the synthesis of mesitylene

molybdenum tricarbonyl was not clear because the product turned out to be black.

However, after taking IR and NMR spectra, they showed that the black solids contained
the wanted final product.
Conclusion:
Through these three syntheses, it was found from the IR spectra that

cycloheptatriene creates the strongest back bonding effect on the carbonyls, while
mesitylene creates the weakest back bonding. From the 1H NMR spectra,

cycloheptatriene was observed to have the largest change in chemical shift up field, while
hexametheylbenzene showed a downfield change in chemical shift. Although these

results were different from what was expected, they can be understood. Cycloheptatriene
created the strongest back bonding because the electrons in the ring are not delocalized,
allowing a direct donation of electrons to the metal.
References:

Angelici, R. J. Preparation and Characterization of Mesitylene Tricarbonyl Molybdenum

(0) Journal of Chemical Education 1968, 45, 119-120.

Price, J. T.; Sorensen T. S. Nuclear magnetic resonance study of arene metal tricarbonyl
complexes Can. J. Chem 1968, 46, 515-522.