OBJECTIVE

1. To prepare an organomolybdenum (0) compound

2. To determine its structure by spectroscopic method
3. To prepare a substitution product

INTRODUCTION

Part B: Substitution Reaction of (1,3,5trimethybenzene)tricarbonylmolybdenum

(0) with Triphenylphosphine

The mesitylene group is bonded to the molybdenum centre through delocalized π - electron
ring. The aromaticity of the ligand is indicated by its ability to undergo Friedel-Crafts
reactions, e.g. with acetyl chloride. Such reactions are slower on the
tricarbonyl(mesitylene)molybdenum than benzene, which suggests that the electron density
contributes to the bonding to the molybdenum.

The tricarbonyl(mesitylene)molybdenum complex adopts a near C3v symmetry with the

three carbonyl groups occupying an eclipsed arrangement relative to the three methyl
groups. The mesityl group is η6 to the molybdenum central metal atom, which lies 0.009 Å
away from the ring centre and the methyl groups on the benzene are bent out of plane by
0.035 Å due to steric interaction with the carbonyl groups.

Ligand substitution reactions are essential for the use of transition metal organometallic
compounds. Therefore, it is important that we know what factors affect the rates of reaction
and why. Much information, both qualitative and quantitative, is available on the reactivity
of organometallic compounds [19]. What is needed are more detailed kinetic studies that give
information on the mechanisms of ligand substitution, and on what factors contribute to rates
of reaction in these systems.
INTRODUCTION

In the second part of the lab, we are interested in creating the triphenylphosphine analog of
the mesitylene molybdenum tricarbonyl complex from Triphenylphosphine hexacarbonyl.
Triphenylphosphine is a common organophosphorus compound with the formula P(C₆H₅)₃ -
often abbreviated to PPh₃ or Ph₃P. It is widely used in the synthesis of organic and
organometallic compounds. PPh₃ exists as relatively air stable, colorless crystals at room
temperature.

The arene can be displaced by the trimethylphosphite via a SN2 type mechanism to give
the fac-tricarbonyltris(trimethyl phosphite)molybdenum.

The tricarbonyl(mesitylene)molybdenum complex can be used an electron donor.

Tricarbonyl(mesitylene)molybdenum can act as a catalyst for the polymerisation
of phenylacetylene. The Molybdenum complex is activated with an oxidant such as chloranil.
The result of the charge transfer facilitates ring slippage and the mesitylene group changes
from η6 to η2 this allows the phenylacetylene monomer units to bind to the metal centre.
PROCEDURES & OBSERVATIONS

0.2g (C6H3Me3)Mo(CO)3 and 0.8g triphenylphosphine were weighed into a round bottomed
flaSK (50cm3). The reactants were broken up in Ca. 25cm^3 heptane, where light yellow
arrangement with white encourage was observed. The little measure of white accelerate was
insoluble in heptane. The blend was then refluxed (110 degree Celsius) and mixed for around
40 minutes. After around 20 minutes, dark hasten were seen as response continue. The blend
was left to cool to room temperature. Subsequently the product was sifted and washed with
heptane. At this stage, grey precipitate was observed, and the item was dried by suction. The
weight of the product was recorded, and an example was submitted for C and H
microanalysis.

Colour of mixture at3.19pm colour of mixture at 3.33pm

Chemical Analysis & Discussion

Part B: Substitution Reaction of (1,3,5trimethybenzene)tricarbonylmolybdenum

(0) with Triphenylphosphine

1. C, H microanalysis. Determine the carbon and hydrogen content.

Chemical Analysis & Discussion

2. Infrared Spectrum. Record the infrared spectrum of your product. Where

possible assign the absorption bands to the particular molecular vibration
involved.

Infrared spectroscopy involves the interaction of

infrared radiation with matter. It covers a range
of techniques, mostly based on absorption
spectroscopy. As with all spectroscopic
techniques, it can be used to identify and study
chemicals.

From the experimental infrared spectrum, we can see there are few peaks that are significant
in terms of their intensity and type of bond. From the first peak from left, it shows the
wavenumber of 3059.27, from there we know that the appearance is medium and has C-H
stretching. While at the wavenumber of 2157.21, has a medium to weak appearance with
C(triplebond)C stretching.
Chemical Analysis & Discussion

The IR spectrum showed a strong peak around 142.66 indicative of antisymmetrical C-O
stretching and a medium peak around 2942 cm-1 of area 9.111 cm-1 indicative of
symmetrical C-O stretching. These areas were used to calculate a OC-Mo-CO bond angle of
108.32°. The strong peak accounts for antisymmetrical stretching of the carbonyls and the
medium peak accounts for symmetrical stretching of the carbonyls.
Calculation & Discussion
Question & Discussion

1. Why is the first preparation carried out under a nitrogen atmosphere?

From the above statement, we know that the intermediate compound can be easily
oxidised under a nitrogen atmosphere. This will help to form a much more stable
compound.

2. Account for the difference between the chemical shifts in the HNMR spectra of
mesitylene and (mesitylene)Mo(CO)3.

The chemical shift of aromatic ring is at 7.27 ppm (downfield) because of the ring-
current effect. The six Pi-electrons in benzene produce a net current that will give rise
to a deshielding field that is the induced field will tend to reinforce the external
magnetic field whereas the chemical shift of benzyl ligands becomes smaller because
benzyl ligands possess a Pi-system which is able to act as a weak electron donor
towards the metal centre. Therefore the rings current effect is less which results in
uofield shift of about 5-6ppm.
3. How would you expect the u(CO) absorptions in the series of compounds
(C6H6)Mo(CO)3, (C6H3Me3)Mo(CO)3 and (C6Me6)Mo(CO)3 to vary?

u(CO) absorptions decreases in the series of compounds (C6H6)Mo(CO)3,

(C6H3Me3)Mo(CO)3 and (C6Me6)Mo(CO)3 because Me is an electron releasing
group, therefore (C6Me6) is an electron rich complex. The extensive back bonding
strengthen the M-CO bond. Therefore, it lowers the C-O bond order and thereby CO
stretching frequency.

4. Explain the course of the substitution reaction with Ph3P and derive possible
structures for the product.