Preparation, Characterization and Substitution Reaction of 1,3,5-Trimethylbenzene

Tricarbonyl Molybdenum (0), Mo[η6-C6H3(CH3)3](CO)3

Christina Aprilia

20000160

Organotransitional Metal Chemistry

Department of Applied Chemistry

2020
1. Chemical Assessment
2. Flowchart
Synthesis of 1,3,5 – trimethybenzene tricarbonyl molybdenum (0) complex, Mo[η6-
C6H3(CH3)3](CO)3

Start

Reflux system is assembled

Weighed 2.0 g molybdenum

hexacarbonyl

Placed in a round bottomed flask (50-100 mL)

10 mL 1,3,5-trimethylbenzene (mesitylene) is added

Flushed the apparatus with a moderate stream of

nitrogen (5 mnt)

Turned off the nitrogen and closed the stopcock on the flask

Boiled the mixture vigorously on a heating mantle (30 minute)

Pushed back Mo(CO)6 sublime into the flask

Large Yes
quantities of
Mo(CO)6

No
Removed the heating
mantle
Immediately turned on the stream of N2

Turned off the N2 when the solution has cooled

15 mL petroleum ether is added to the flask

Dissolved in a small amount of dichloromethane the product

 Filtered and washed with petroleum ether

Dried the product by drawing air through the glass frit

Recorded the yield of the product

Finish

3. Objectives
 To determine yield percentage of 1,3,5 – trimethylbenzene tricarbonyl molybdenum
(0) complex
 To determine the structure of synthetized product by analyzing product with FTIR, C-
H analysis and NMR

4. Introduction
Molybdenum hexacarbonyl is synthesize molybdenum that attached to six
carbonyl ligand is commonly used as a precursor to organometal transition compounds.
Furthermore, mesitylene is trivial name of 1,3,5- C 6H3(CH3)3 as a ligand that will react
with molybdenum hexacarbonyl (Kose, 2013). Mesitylene which is more stable than
benzene itself. In some aspects, benzene acts like three alkenes and donates six electrons
to the metal. Benzene and its derivatives do often react to displace three donor ligands.
The three ligands that will displace three donor ligands e.g. carbonyl ligands. But
mesitylene forms more stable than benzene, it will be used as the aromatic ligand
(Girolami & Angelici, 1999).

Fig 1. Structure of Mo[η6-C6H3(CH3)3](CO)3

 This reaction use reflux system under nitrogen gas pressure condition followed by
precipitation and recrystallization process.

Fig 2. Synthesis reaction of Mo[6 -C6H3 (CH3)3](CO)3

Metal-arene complex is interesting because it can be considered to be an

octahedral rather than a tetrahedral complex. This is because the OC-Mo-CO bond
angles are close to 90° instead of the expected 109.5° for tetrahedral. In order to
determine the structure of said substance from its 1H NMR, the peaks must be compared
to the same spectrum of mesitylene for an indication of identical methyl group peaks and
downfield shifting a peak indicative of protons attached directly to the ring. The IR
spectrum of [1,3,5-C6H3(CH3)3]Mo(CO)3 can be analyzed for peaks indicative of
symmetrical and asymmetrical carbonyl stretching, whose areas can be used to calculate
the bond angle between the carbonyl groups attached the to metal (Girolami & Angelici,
1999).
5. Procedure and Observation
A. Experimental set up and procedure: Synthesis of 1,3,5 – trimethybenzene tricarbonyl
molybdenum (0) complex, Mo[η6-C6H3(CH3)3](CO)3
 The reflux system assembled as shown in the fig 1.
 Weighed ~2.0 g molybdenum hexacarbonyl
 Placed in a round bottomed flask (50-100 mL)
 10 mL mesitylene are added
 Flushed the apparatus with moderate stream of N2 (~5 minutes)
 Turned off the N2 and closed the stopcock on the flask
 Boiled the mixture vigorously on a heating mantle (~30 minutes)
 Pushed the Mo(CO)6 solid sublime back to the flask using glass rod
 Removed the heating mantle
 Turned on the N2 stream
 Let the solution being cooled to room temperature
  Turned off the N2
 Added petroleum ether (15mL) to the flask
 Purified the precipitated by dissolved a small amount of dichloromethane
 Filtered and added petroleum ether to the solution to precipitate the product
 Filtered and washed with petroleum ether
 Dried the product by drawing air through the glass frit.
 Recorded the yield of your product
 Characterized the result using FTIR analysis, C-H analysis, and H-NMR
analysis

B. Observation
Experimental Observations
Mixture of molybdenum hexacarbonyl and mesitylene during warming up
process has different colors as shown in the table below.
Table 1. Color observation during warming up solution

Time heating Color Observations

(minutes)
0 white

10 yellow

20 dark
 30 greenish dark

The color of obtained product is pale yellow as shown below.

Fig 3. Product of Mo[η6-C6H3(CH3)3](CO)3 synthesis

C-H Analysis

The data which used is group 1 (standard:sulfanilamide), group 2 (sample 1),

and group 3 (sample 2). Each result showed there is no nitrogen content in the sample.
Sample showed contain of C, H, and S. Sulphur content actualy not present in the
sample, this is affected because the devices has been used frequently to analyze
sample which contain sulphur.
FTIR Spectrum

The IR spectrum showed a strong peak around 1855,87 cm -1 indicative of C=O

stretching. Aromatic structure has shown by the presence of overtones peak around 2000
cm-1. C-H stretching peak is shown in 2922,98 cm -1 which has weak intensity and
bending (in plane) in 1440,08 showed a strong, sharp, and less intense, then bending (out
of plane) in 585,5 and 611,64 cm-1 as showed strong, sharp, and intense.
H-NMR

H NMR result explains how many atom hydrogen

Peak 1: chemical shift 1.5 ppm, singlet, no neighbor. Based on chemical shift, the
type of proton is CH3. Its position is shown low peak

Peak 2: chemical shift 2.2 ppm, singlet, no neighbor. Based on chemical shift, the
type of proton is CH3 bonded to benzylic group. Its position is shown strong peak

Peak 3: chemical shift 5.2 ppm, singlet, no neighbor. Based on chemical shift, the
type of proton is vinylic (H is attached to alkene C). Its position is shown medium
peak

Peak 4: chemical shift 6.8 ppm, singlet, no neighbour. Its position is shown weak peak

Peak 5: chemical shift 7.2 ppm, singlet, no neighbor Based on chemical shift, the type
of proton is aromatic (H is on phenyl ring). Its position is shown medium peak
6. Result
 Weight of bottle :10.1528 grams
 Weight of bottle + product :10.1759 grams
 Weight of product : 0.0231grams

7. Calculation of Yield of Product

Mass of product
 Moles of products :
MM of Trimethylbenzene Tricarbonyl Molybdenum (0)
0.0231 g rams
:
300.18 g / mol
: 7,6953 x 10-5 mol
Massof Mo (CO) 6
 Maximum moles of product :
MM of Mo (CO) 6
2 grams
:
264.0206 g /mol
: 7.5751x 10-3 mol
 Maximum gram of product : 2 grams
0.0231 grams
 Mass of product obtained % yield of product: x 100 %
2 grams
: 1.155%
8. Chemical Analysis
 C, H microanalysis to determine the carbon and hydrogen content.

Mass Carbon, C Nitrogen, Hydrogen,H Sulphur,S

(mg) (%) N (%) (%)
(%)
Run standard 2,074 47,6505 0 3,8111 0,2279
(Sulfanilamide)
Run sample (1) 2,078 47,4804 0 3,8479 0,1258
Run sample (2) 2,266 47,3356 0 3,8317 0,0793
Avarage of sample 2,172 47,408 0 3,8398 0,10255

Molar mass of [1,3,5-C6H3(CH3)]Mo(CO)3 = 300.18 g.mol-1

Molar mass of element = (percentage:100) x molar mass of product
Molar mass of carbon = (47,408:100) x 300.18g.mol-1
= 142,3093g.mol-1
Molar mass of nitrogen = (0:100) x 300.18g.mol-1
 =0
Molar mass of hydrogen = (3,8398:100) x 300.18g.mol-1
= 11,5263g.mol-1

Molar mass of sulphur = (0,10255:100) x 300.18g.mol-1

= 0,3078g.mol-1
It was confirm the total molar mass of carbon and hydrogen in the product
Molar mass of carbon = 9 atom C from 1,3,5-C6H3(CH3) + 3 carbon from
carbonyl grup
= [(9 x 12.01 g/mol) + (3 x 12.01 g/mol)]
= 144.12 g/mol (~ 142.3093 g/mol)
Molar mass of hydrogen = 3 atom H from remain in phenyl + 9 atom from 3
methyl in mesitylne
= [(3 x 1.008 g/mol) + (9 x 1.008 g/mol)]
= 12.096 g/mol (~11,5263g.mol-1)
 Infrared spectrum

Table 2. Analysis of absorption peak of FTIR

Functional Absorption Type of vibration Intensity
group
2922,98 stretch weak
1440,08 bending strong, shrap, less
C-H intense
585,50 bending strong, shrap,
intense
C=C 1518,11 and stretch weak
1546,31
C=O 1855,87 stretch strong, less intense
Overtones ~2000 - sharp, weak, multi
band
  H-NMR Spectrum
Analysis absorption peak to the structure:

Peak 1: chemical shift 1.5 ppm, singlet, no neighbor. Based on chemical shift, the type
of proton is CH3. Its position is shown with medium peak (red)

Peak 2: chemical shift 2.2 ppm, singlet, no neighbor. Based on chemical shift, the type
of proton is CH3 bonded to benzylic group. Its position is shown with strong
peak (red)

Peak 3: chemical shift 5.2 ppm, singlet, no neighbor. Based on chemical shift, the type
of proton is vinylic (H is attached to alkene C). Its position is shown with
medium peak (blue)

Peak 4: chemical shift 6.8 ppm, singlet, no neighbour. Its position is shown with weak
peak

Peak 5: chemical shift 7.2 ppm, singlet, no neighbor Based on chemical shift, the type
of proton is aromatic (H is on phenyl ring). Its position is shown with
medium peak (blue)

9. Discussion
Synthesis of of 1,3,5 – trimethylbenzene tricarbonyl molybdenum (0) complex is
made from reaction between molybdenum hexacarbonyl (Mo(CO)6) and mesitylene
(1,3,5- C6H3(CH3)3) as precursors. The reaction aims to substitute mesitylene into three
of carbonyl group attached to molybdenum to form a product. The solution had been
kept under nitrogen to prevent decomposition of the product i.e. reaction between oxygen
gas and metal. Because nitrogen gas is inert, flowing nitrogen gas in reflux system can
hinder oxygen contaminating and it will not interfere with the reaction. The product
obtained 0.0231 grams and 1.155% yield based on the amount of Mo(CO)6 used, which
was the limiting reagent in the reaction. The poor amount of product may be caused by
exposure to the air when push the solid (Mo(CO) 6 sublime) back into the flask using a
glass rod. The color of product is pale yellow crystalline. It has high solubility in a non-
 polar solvent, that’s why in recrystallization proses of this compound use
dichloromethane as a non-polar solvent and use petroleum ether to precipitate
(Nesmeyanov, 1974).
Chemical analysis which used in this experiment is C, H microanalysis, infrared
spectrum, and H-NMR. C, H microanalysis shows carbon and hydrogen content in the
product by determining in the percentage. The percentage of C and H is 47,408 % and
3,8398 % respectively. Sulphur content is present in the analysis may be affected by
instrument contaminants. This is due to the instrument has been used frequently to
analyze sample which contains sulphur. But this value can be neglected because very
small as much as 0,10255%. Molar mass of carbon and hydrogen are obtained
142,3093g.mol-1 and 11,5263g.mol-1 respectively that has similarity with theoretical
molar mass of C and H in the compound. The IR spectrum showed a strong peak around
1855,87 cm-1 indicative of C=O stretching. Aromatic structure has shown by the
presence of overtones peak around 2000 cm-1. C-H stretching peak is shown in 2922,98
cm-1 which has weak intensity and bending (in plane) in 1440,08 showed a strong,
sharp, and less intense, then bending (out of plane) in 585,5 and 611,64 cm-1 as showed
strong, sharp, and intense. There are three main peaks were observed in H-NMR
spectrum, 2.2 ppm was indicative the type of proton is CH3 bonded to benzylic group.
Its position is shown at a strong peak. The second peak at 5.2 ppm was indicative the
type of proton is vinylic (H is attached to alkene C). Its position is shown medium peak.
The third peak was observed at 7.2 ppm indicate the type of proton is aromatic (H is on
phenyl ring). Its position is shown medium peak.

10. Conclusion
The conclusions of this experiment are:
1) Percent yield of the product is 1.155%. The poor amount of product may be caused
by exposure to the air when push the solid (Mo(CO)6 sublime) back into the flask
using a glass rod.
2) C, H microanalysis spectrum gave percentage of carbon and hydrogen 47,408 % and
3,8398% respectively. Molar mass of carbon and hydrogen are obtained 142,3093
g.mol-1 and 11,5263 g.mol-1 respectively that has similarity with theoretical molar
mass of C and H in the compound. Sulphur content is present in the analysis may be
affected by instrument contaminants. This is due to the instrument has been used
frequently to analyze sample which contains sulphur. But this value can be neglected
 because very small as much as 0,10255%. H-NMR spectrum of the product showed
peaks at 2.25 ppm indicate CH3 bonded to a benzylic group and 5.23 ppm indicate
proton is vinylic (H is attached to alkene C). While the H-NMR spectrum of H in
mesitylene gave peaks at 6.78 ppm and 2.25 ppm, both in ratios of 9:3, respectively.
This confirms the product consists of methyl groups and single protons attached to
the ring. The IR spectrum showed a strong peak around 1855,87 cm-1 indicative of
C=O stretching. Aromatic structure has shown by the presence of overtones peak
around 2000 cm-1. C-H stretching peak is shown in 2922,98 cm-1 which has weak
intensity and bending (in plane) in 1440,08 showed a strong, sharp, and less intense,
then bending (out of plane) in 585,5 and 611,64 cm-1 as showed strong, sharp, and
intense.

11. References
Girolami, G. S., Rauchfuss, T. B., & Angelici, R. J. (1999). Synthesis and Technique
in Inorganic Chemistry: A Laboratory Manual. (3 ed.) Sausalito, CA:
University Science Books.

Kose, E., Atac, A., Karabacak, M., Nagabalasubramanian, P. B., Asiri, A. M., &
Periandy, S. (2013). FT-IR and FT-Raman, NMR and UV spectroscopic
investigation and hybrid computational (HF and DFT) analysis on the
molecular structure of mesitylene. Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, 116, 622–634.doi:10.1016/j.saa.2013.07.070 

Nesmeyanov, A. N., Krivykh, V. V., Kaganovich, V. S., & Rybinskaya, M. I.

(1974). Synthesis of arenemolybdenum tricarbonyl complexes. Bulletin of the
Academy of Sciences of the USSR Division of Chemical Science, 23(4), 827–
829.doi:10.1007/bf00923510