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

trimethybenzene)tricarbonylmolybdenum (0) with Triphenylphosphine

Christina Aprilia

20000160

Organotransitional Metal Chemistry

Department of Applied Chemistry

2020
1. Chemical Assessment
No. Chemical Approx. Assessme Hazard First Aid Measured
Amount nt
1. (1,3,5 - 0.2 g H=4 Fatal if Eye Contact : Check for
trimethybenzene) swallowed and remove any contact
F=1
tricarbonyl lenses. In case of contact,
Fatal in contact
molybdenum R=0 immediately flush eyes
with skin
with plenty of water for at
PPE = -
Fatal if inhaled least 15 minutes. Get
medical attention if
irritation occurs
Skin Contact : Wash with
soap and water. Cover the
irritated skin with an
emollient. Get medical
attention if irritation
develops.
Inhalation : If inhaled,
remove to fresh air. If not
breathing, give artificial
respiration. If breathing is
difficult, give oxygen. Get
medical attention.
2 Triphenylphosphine 0,8 g H=2  Harmful if Eyes: In case of contact,
swallowed. immediately flush eyes
F=1  May cause with plenty of water for a t
R=0 an allergic least 15 minutes. Get
skin medical aid.
PPE = - reaction. Skin: In case of contact,
 May cause
flush skin with plenty of
damage to
water. Remove
organs
(Central contaminated clothing and
nervous shoes. Get medical aid if
system, irritation develops and
Peripheral persists. Wash clothing
nervous before reuse.
system) Ingestion: If swallowed,
through do not induce vomiting
prolonged unless directed to do so by
or repeated medical personnel. Never
exposure. give anything by mouth to
 May cause an unconscious person.
long lasting
Get medical aid.
harmful
 effects to Inhalation: If inhaled,
aquatic life. remove to fresh air. If not
breathing, give artificial
respiration. If breathing is
difficult, give oxygen. Get
medical aid.
3 Heptane 25 mL H=3  Highly Eye Contact : Rinse
flammable immediately with plenty of
F=3 liquid and water, also under the
R=0 vapour eyelids, for at least 15
 May cause minutes. Get medical
PPE = - drowsiness attention.
or dizziness
 May be Skin Contact : Wash off
fatal if immediately with plenty of
swallowed water for at least 15
and enters minutes. Obtain medical
airways attention.
 Causes skin
irritation Ingestion : Move to fresh
Causes air. Do not use mouth-to-
serious eye mouth method if victim
irritation ingested or inhaled the
substance; give artificial
respiration with the aid of
a pocket mask equipped
with a one-way valve or
other proper respiratory
medical device. Obtain
medical attention. Risk of
serious damage to the
lungs. If not breathing,
give artificial respiration.
Inhalation : Do not induce
vomiting. Call a physician
or Poison Control Center
immediately. If vomiting
occurs naturally, have
victim lean forward.
2. Flowchart
Synthesis of 1,3,5 – trimethybenzene tricarbonyl molybdenum (0) complex, Mo[η6-
C6H3(CH3)3](CO)3

Start

Reflux system was assembled as shown in the figure 1 below

Approximately weighed 0.2 g (C6H3Me3)Mo(CO)3

(synthesized in part A) and 0.8 g triphenylphosphine

Placed in a round bottoed flask (50mL) fitted

with refluxcondenser

The reactant were dissolved in 25 mL of heptane and the

mixture was then refluxed (110oC) for 30 minutes with
strring

Precipitation of product occured as the reaction proceeds

The mixture was then left to cool to roomtemperature

Once cooled, the product was filteretd and washed with

heptane and subsequently dried by suction

The weight of the product was recorded and the percentage

yield was calculated

Finish

3. Objectives
 To subtitute mesitylene attached to organomolybedenum (0) by triphenylphosphine
 To determine the weight and percentage of organomolybedenum (0)
 To confirm the organomolybdenum (0) compund via C-H analysis and FTIR
4. Introduction
Synthesis of triphenylphosphine tricarbonyl molybdenum is made from reaction
between (1,3,5–trimethybenzene) tricarbonylmolybdenum and triphenylphosphine by
using reaction substitution. Substitution reaction also known as single displacement
reaction or single substitution reaction is a chemical reaction during which one functional
group in a chemical compound is replaced by another functional group (March, 1985). In
this reaction, mesitylene attached to molybdenum is replaced by triphenylphosphine. The
reaction of this experiment is shown by figure below.
Substitution reaction:

PPh3
A B C D

5. Procedure and Observation

 Reflux system was assembled as shown in the figure 1 below
 Approximately weighed 0.2 g (C6H3Me3)Mo(CO)3 (synthesized in part A) and
0.8 g triphenylphosphine
 Placed in a round bottoed flask (50mL) fitted with refluxcondenser
 The reactant were dissolved in 25 mL of heptane and the mixture was then
refluxed (110oC) for 30 minutes with strring
 Precipitation of product occured as the reaction proceeds
 The mixture was then left to cool to roomtemperature
 Once cooled, the product was filteretd and washed with heptane and
subsequently dried by suction
 The weight of the product was recorded and the percentage yield was calculated

Figure 1. Experimental set up of the reflux system

A. Observation
 A pale-yellow solution with white precipitate was observed when (1,3,5-
trimethylbenzene)tricarbonylmolybdenum (0) was mixed with
triphenylphospine
 Colour of the solution was observed to change from pale-yellow to pale-
brown at 70-83oC
 The colour of the solution turned to darker brown at 94oC
 The solution starts to form bubbles at 95oC and bubbling became more
vigorously at 98oC
 The colour of the solution became light brown at 99oC
 A light brown products was obtained after being filtered, washed with heptane
and dried

The color observation during subtitution reaction:

Fig 2. Mo[η6-C6H3(CH3)3](CO)3 synthesis product in part A (yellow green) and

PPh3 (white)

Fig 3. The color of product obtained (grayish-brown)

C-H Analysis

Trial Mass of sample C% H%

(mg)
1 1.7300 65.77 4.339

2 2.1520 63.49 4.030

C-H analysis shows carbon percentage in the product 65.77 % and 63.49% and
hidrogen as much 4.339 % and 4.030 %.

FTIR Spectrum

The IR spectrum showed a strong peak around 1888.81 cm-1 and 1809.34 cm-
1
indicative of C=O stretching. Aromatic structure has shown by the presence of
overtones peak around 2000 cm-1. Triphenylphosphine bending peak is shown at 493.92,
510.30, 532.81, 542.00, 617.37, and 624.64 cm-1 which has sharp and strong intense
peak (in literature, 683 or 515-491 cm-1) (Clark, Flint & Hempleman, 1987). C-H
stretching peak is shown around 3000 cm-1 which has weak intensity and small.
6. Result
 Weight of bottle :82.9666 grams
 Weight of bottle + product :83.3343 grams
 Weight of product : 0.3677 grams

7. Calculation of Yield of Product

 Moles of products :

: 3.8031 x 10-4 mol

 Moles of products (theoretical)

PPh
A B C D

Mass Molar Mass Number of moles (mole)

(g) (g/mole)
A 0.2 300.18 6.6 x 10-4
B 0.8 262.29 3.05 x 10-3

A + 3B  C + D

Initial : 6.6 x 10-4 3(3.05 x 10-3)

Reaction : -6.6 x 10-4 -6.6 x 10-4 +6.6 x 10-4 +6.6 x 10-4
Equilibrium: 0 8.4 x 10-3 6.6 x 10-4 6.6 x 10-4

 Maximum mass of products (C) : moles of C x MM of C

: 6.6 x 10-4 moles x
: 0.6381grams

 Mass of product obtained % yield of product: x 100 %

: 57.6241%
8. Chemical Analysis
 C, H microanalysis to determine the carbon and hydrogen content.

Mass (mg) Carbon, C Hydrogen,H

(%) (%)

Run sample (1) 1.7300 65.77 4.339

Run sample (2) 2.1520 63.49 4.030

Avarage of sample 1.9410 64.63 4.1845

Molar mass triphenylphosphine tricarbonyl molybdenum (0) = 966.83 g.mol-1

Molar mass of element = (percentage:100) x molar mass of product
Molar mass of carbon = (64.63:100) x 966.83g.mol-1
= 624.8622 g.mol-1
Molar mass of hydrogen = (4.1845:100) x 966.83 g.mol-1
= 40.4570 g.mol-1
It was confirm the total molar mass of carbon and hydrogen in the product
Molar mass of carbon = 3 atom C from CO + 54 carbon from PPh3
= [(3 x 12.01 g/mol) + (54 x 12.01 g/mol)]
= 684.57 g/mol (~ 624.8622 g/mol)
Molar mass of hydrogen = 45 atom H from PPh3
= (45 x 1.008 g/mol)
= 45.36 g/mol (~40.4570 g.mol-1)
  Infrared spectrum

Table 2. Analysis of absorption peak of FTIR

Functional group Absorption (cm-1) Type of vibration Intensity
3000 stretch weak and
C-H 1477.13 bending strong, shrap, less
1432.47 intense
C=O 1886.61 stretch medium intense
1809.34
Overtones ~2000 - sharp, weak, multi
band
Triphenylphosphine 493.92 bending sharp, strong,
510.30 intense
532.81
542.00
617.37
624.64

9. Discussion
Synthesis of triphenylphosphine tricarbonyl molybdenum is made from reaction
between (1,3,5–trimethybenzene) tricarbonylmolybdenum and triphenylphosphine by
using reaction substitution. The reaction aims to substitute mesitylene by
triphenylphosphine 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.
Based on some given spectra in part of observation data and calculation, FTIR
result shows that analyzed product contain triphenylphospine functional group and CO
ligand. Both PPh3 and CO ligand are shown by intense peaks. Some literature gives
different value because of back-bonding of compound, this is due to PPh3 is strong phi
acceptor ligand that tend more back-bonding from metal, thus affect wavenumber of CO
decrese. This FTIR result indicate that synthesized product has same functional group to
desired product (Stuart, 2004). The product was obtained 0.3677 grams and 57.6241%
 yield. The poor amount of product may be caused by exposure to the air. The color of
product is grayish-brown.
Chemical analysis which used in this experiment is C, H microanalysis and
infrared spectrum. C, H microanalysis shows carbon and hydrogen content in the product
by determining in the percentage. The percentage of C and H are 64.63 % and 4.1845%
respectively. Molar mass of carbon and hydrogen are obtained 624.8622 g.mol-1 and
40.4570 g.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 1888.81 cm-1 and 1809.34
cm-1 indicative of C=O stretching. Aromatic structure has shown by the presence of
overtones peak around 2000 cm-1. Triphenylphosphine bending peak is shown at 493.92,
510.30, 532.81, 542.00, 617.37, and 624.64 cm-1 which has sharp and strong intense
peak (in literature, 683 or 515-491 cm-1) (Clark, Flint & Hempleman, 1987). C-H
stretching peak is shown around 3000 cm-1 which has weak intensity and small.

10. Conclusion
The conclusions of this experiment are:
1) Triphenylphosphine tricarbonyl molybdenum is made from reaction between (1,3,5–
trimethybenzene) tricarbonylmolybdenum and triphenylphosphine by using reaction
substitution with color observed greenish brown.
2) Triphenylphosphine tricarbonyl molybdenum was obtained 0.3677 grams and
57.6241% yield.
3) The percentage of C and H are 64.63 % and 4.1845% respectively. Molar mass of
carbon and hydrogen are obtained 624.8622 g.mol-1 and 40.4570 g.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 1888.81 cm-1 and 1809.34 cm-1 indicative of
C=O stretching. Aromatic structure has shown by the presence of overtones peak
around 2000 cm-1. Triphenylphosphine bending peak is shown at 493.92, 510.30,
532.81, 542.00, 617.37, and 624.64 cm-1 which has sharp and strong intense peak (in
literature, 683 or 515-491 cm-1) (Clark, Flint & Hempleman, 1987). C-H stretching
peak is shown around 3000 cm-1 which has weak intensity and small.
11. Question
1) Why is the first preparation carried out under a nitrogen atmosphere ?
The using of N2 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
2) Account for the difference between the chemical shifts in the HNMR spectra of
mesitylene and (mesitylene)Mo(CO)3!
Mesitylene has singlet peak at about 2.34 ppm (nine methyl hydrogens on both the
free mesitylene) and 7.16 ppm (three aryl hydrogens on ring free mesitylene).
While molybdenum tricarbonyl gives the singlet at about 2.21 ppm (nine methyl
hydrogens on both the mesitylene ligand) and 5.17 ppm (three aryl hydrogens on
ring mesitylene ligand).
3) How would you expect the v(CO) absorptions in the series of compounds
(C6H6)Mo(CO)3, (C6H3Me3)Mo(CO)3 and (C6Me6)Mo(CO)3 to vary?
Methyl is a strong σ donors and good π acceptor, so if attached to benzene ring as
a ligand to metal, methyl in benzene (mesitylene) will “pushed” electron to metal
orbital make the Δoct larger contributes to v(CO) also will be smaller, because
effect of LMCT(Ligand to Metal Charge Transfer) getting stronger make the bond
C=O weaker, so :
V(CO) values cm-1 :(C6H6)Mo(CO) > (C6H3Me3)Mo(CO)3 > (C6Me6)Mo(CO)3.
4) Explain the course of the substitution reaction with Ph3P and derive possible
structures for the product!
Triphenyl is 2 electron ligands but mesitylene is 6 electron ligand so that
triphenylphospine can replace mesytilene. Furthermore, triphenyl is strong phi-
acceptor ligand to the metal then easier to subtitute mesitylene. Possible structure:
12. References:

Clark, R. J. H., Flint, C. D., & Hempleman, A. J. (1987). F.t.i.r. and Raman spectra of
triphenylphosphine, triphenylarsine, triphenylstibine, and dibenzylsulphide.
Spectrochimica Acta Part A: Molecular Spectroscopy, 43(6), 805–
816.doi:10.1016/0584-8539(87)80223-4

March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and

Structure (3rd ed.), New York: Wiley, ISBN 0-471-85472-7

Stuart, B., 2004. Infrared Spectroscopy: Fundamentals and Applications. England:

John Wiley & Sons Ltd.
13. Appendices