Name: Gerry Mark S.

Gubantes Date Performed: September 29, 2017

Groupmate: Christine Joy de Rama Date Submitted: October 13, 2017
Group No.: 1

Exercise 4
Oxomolybdenum Chemistry

I. Results and Discussion

Molybdenum is a 2nd row element of transition metals involved. It is readily convertible to
several oxidation states, and has the ability to form stable bonds with N, O, and S. Molybdenum,
in the form of oxomolybdenums, plays important biological functions as a catalyst for many
biochemical reactions. The oxo-ligand in oxomolybdenum can stabilize high-valent metal centers
through both π and σ base interactions of the d-orbitals and the ligand p-orbitals resulting in high
susceptibility to nucleophilic and electrophilic reactions. In enzyme catalysis such as in nitrate
reductase, the molybdenum proves the electronic pathways necessary for the biochemical
reaction due to the stability of the Mo IV and VI oxidation levels with terminally-bound ligands
(Holm, 1987).
Oxo complexes dominate the high valent chemistry of early transition metals.
Oxomolybdenum complexes can undergo oxygen transfer reactions, which can either be
nucleophilic or electrophilic. A nucleophilic reaction is accompanied by a change in the oxidation
states of the reactant (Arzoumanian, 1998).

A nucleophilic reaction involves the change in the oxidation state of the metal. It is
characterized by the interaction between a nucleophile to an electron – deficient atom.
Nucleophilic reactions may involve redox reactions with oxygen atom transfer called the Oxygen
Atom Transfer (OAT) reactions or oxo – transfer reaction. When a metal undergoes OAT, this will
result in an increase of +2 in the oxidation number upon oxidation, or a decrease of -2 upon
reduction. The OAT is a two – electron process. There are two types of Oxygen Atom Transfer
(OAT): primary or secondary. The primary type is characterized by the change in oxidation state
of the metal alone as shown below (Arzoumanian, 1998).
The mechanism is presented below.

Figure 4.1. Mechanism for the nucleophilic reaction with Mo complex.

An example of this OAT reaction type are the reactions between S – and N –oxides, peroxides
and dioxygen with oxo – Mo(IV) complexes.
On the other hand, the secondary type of oxygen atom transfer (OAT) is the internal redox
reaction or the oxidation of the substrate with accompanying reduction of the metal and ligand.
These reaction types include the nucleophilic reaction between a phosphine and a dioxo – Mo(VI)
compound. This reaction also results in the two – electron reduction of molybdenum and the
simultaneous oxidation of phosphorus (Arzoumanian, 1998).
Meanwhile, for electrophilic reactions, there is an involvement of an SN2 protonation step
that is not accompanied by a redox change. It is used to selectively replace oxo – ligands by
anionic ligands. This type of reaction occurs when an electrophile is drawn towards an electron
rich species. However, this does not change the oxidation state of any chemical species involved
(Arzoumanian, 1998).

The mechanism is shown below

Figure 4.2. Mechanism for the electrophilic reaction with Mo complex.

The first part of the experiment involves the preparation of cis – bis(N,N-
diethyldithiocarbamato)dioxomolybdenum(VI). It was used as an intermediate for the synthesis
of other oxomolybdenum complexes: the purple, red and yellow compounds. Initially,
diethylamine was added to the NaOH solution. Then, carbon disulfide was added and swirled for
10 minutes. The reaction that occurred during this step is shown below:
NH3Et2 + NaOH + CS2 NaS2CNEt2 + H2O (Eqn. 4.1)
Next, sodium molybdate(VI) dehydrate was added to the solution. It served as the source of the
molybdate ion. The reaction mixture was then treated with a solution of 1.30 mL concentrated
HCl in 16.70 mL water added in a dropwise manner over a period of 15 minutes with vigorous
agitation. The reaction is shown below.
2 NaS2CNEt2 + Na2MoO2.2H2O + HCl MoO2(S2CNEt2) + 4 NaCl + 4 H2O (Eqn.4.2)
After the addition of the acid, the precipitate was separated using sintered funnel since a regular
filter paper can be degraded in an acidic environment. The solids in the sintered funnel were then
washed with ethanol, and allowed to dry before weighing. The observations for the synthesis of
the intermediate, cis – MoO2(S2CNEt2)2 is summarized in Table 4.1. The overall reaction for the
synthesis of cis – MoO2(S2CNEt2)2 is as follows:
2NH3Et2 + 2NaOH + 2CS2 + Na2MoO2.2H2O+ HCl MoO2(S2CNEt2)+ 4 NaCl + 4 H2O (Eqn.4.3)

Table 4.1. Observations for the synthesis of cis-MoO2(S2CNEt2)2.

Reagents/Actions Taken Observations
NaOH+H2O Clear solution
+ diethylamine Clear, colorless solution
+ CS2 Globules formed
After swirling for 10 minutes Homogenous clear, yellow solution
+ sodium molybdate(VI) Yellow solution
dihydrate
Brown precipitate formed in the yellow
+ conc. HCl
solution
Filtration:
Filtrate Green solution
Residue Yellow brown precipitate
Washing w/H2O Yellow brown precipitate
Washing w/EtOH Yellow brown precipitate
Drying Yellow brown precipitate
cis-MoO2(S2CNEt2)2 Yellow brown precipitate

The ligand (S2CNEt2)- was synthesized in situ as it decomposes easily, and cannot be isolated on
its own. It can be synthesized easily due to the kinetic stability of the dithiocarbamato ligand but,
since it is not thermodynamically stable, it immediately binds to the central metal upon the
addition of sodium molybdate to the reaction mixture. Vigorous agitation was also done to control
the pH of the solution to avoid the reduction of Mo6+ to Mo5+ and prevent the side reactions
shown below (Holm, 1987; Dirand, Ricard and Weiss, 1976).
The possible sources of errors in this synthesis are the non-vigorous agitation of the mixture
causing the molybdenum to be reduced. This obtained intermediate was then used for the
synthesis of three other oxomolybdenum compounds termed as the purple compound (P), the
red product (R) and the yellow product (Y).

The first product that was synthesized was the purple compound. It was done by filtering
a solution of 0.17g of cis –MoO2(S2CNEt2)2 in 2 mL dichloromethane through a fluted paper. The
supernatant was decanted and separated from the residue. Then, the supernatant was treated
with a solution of 0.05 g PPh3 in 3.5 mL methanol. PPh3 acts as the reducing agent to form MoVI
to MoIV as shown in the reaction below.
MoVIO2(S2CNEt2)2 + PIIIPh3 OMoIV(S2CNEt2)2 + OPVPh3 (eq 4.4)
OMoIV(S2CNEt2)2 + MoVIO2(S2CNEt2)2 Mo2VO3(S2CNEt2)4 (eq 4.5)
Overall Rxn: 2 MoVIO2(S2CNEt2)2 + PPh3 Mo2VO3(S2CNEt2)4 + OPPh3 (eq. 4.6)
This type of reaction is a nucleophilic oxo-transfer where MoVIO2(S2CNEt2)2 acted as the
oxo donor, while OPPh3 acted as the oxo acceptor. The oxidation state in the metal center of the
final product has been increased by 1. This is also a comproportionation reaction where the
molybdenum molecules having different oxidation numbers react with each other. In addition,
the product also exhibits tribochoism wherein it changes color upon the application of mechanical
stress. From the color green, the product can exhibit a purple color when streaked (Dirand, Ricard
and Weiss, 1976).
The mixture was swirled, and it was allowed to stand for 15 minutes. Through suction
filtration, the product was then isolated with a percent yield of 57.02%. The summary of
observations is presented in Table 4.3.
 Table 4.2. Observations on the synthesis of compound P.
Reagents/Actions Taken Observations
cis-MoO2(S2CNEt2)2 + dichloromethane Brown mixture

Filtration:

Filtrate Brown solution

Residue Few brown solids

+PPh3 to filtrate Purple mixture

Swirl and stand for 15min Purple mixture

Filtration:

Filtrate Purple solution

Residue Needle-like blue-green to black solids

Washing with methanol Needle-like blue-green to black solids

Dry Needle-like blue-green to black solids

In the synthesis of compound R, 0.33 g cis – MoO2(S2CNEt2)2 and 0.33 g PPh3 were initially
dissolved in 1.7 mL 1,2-dichloroethane. The mixture was then placed in a micro-reflux set-up.
The reflux was done for 15 minutes. Upon completion of the reflux, the reaction mixture was
poured in a 100-mL Erlenmeyer flask containing 17 mL cold ethanol. Lastly, the mixture was
filtered and the product was washed with minimal ethanol, and then with ether. The product was
isolated with a percent yield of 80.0%. Table 4.4 shows the observations in the synthesis of
compound R.
The PPh3 acts as the reducing agent to reduce MoVI to MoIV. Excess of PPh3 was added to
prevent the oxidation of R in air since PPh3 is more oxidizable than compound R. This was also
the purpose of the reflux setup to prevent the contact of air from compound R. This type of
reaction is a nucleophilic type of oxo transfer. The overall reaction is shown below (Dirand, Ricard
and Weiss, 1976).
MoVIO2(S2CNEt2)2 + PIIIPh3 MoIV(S2CNEt2)2 + OPVPh3 (eq 4.7)

Table 4.4. Observation on the synthesis of compound R.

Reagents/Actions Taken Observations
Cis-MoO2(S2CNEt2)2 + PPh3 Yellow brown solid + white solid pellet
+1,2-dichloroethane Mixture turned violet
Reflux
Mixture after reflux Red violet solution
+ethanol Red violet solution
 Filtration
Filtrate Violet solution
Residue Red precipitate
Wash with EtOH Red precipitate
Wash with ether Red precipitate
Dried Product Red precipitate

Meanwhile for the synthesis of compound Y, it was done by filtering a solution of 0.17 g
cis – MoO2(S2CNEt2)2 in 11.7 mL acetone through a fluted filter paper. The filtrate was treated
with 0.8 mL 12 M HCl and was swirled for 10 minutes. Then, the mixture was allowed to stand in
an ice bath. Then, the product was filtered using a sintered funnel, and washed using 3.5 mL
acetone before it was dried. The product was isolated with a percent yield of 5.47%. Table 4.5.
shows the observations in the synthesis of compound Y.
HCl acted as the source for the chloride ligands, and promotes the electrophilic reaction
leading to the formation of Y. It is possible to form this reaction without PPh3 since this reaction
is an electrophilic type of oxo transfer, unlike the other reactions which are nucleophilic that needs
PPh3 as a reducing agent. This reaction utilizes the a two-step protonation releasing water in the
process. The overall reaction for the formation of compound Y is shown below below (Dirand,
Ricard and Weiss, 1976).
MoVIO2(S2CNEt2)2 + 2 HCl MoVIOCl2(S2CNEt2)2 (yellow) + H2O (eq 4.8)

Table 4.5. Observations on the synthesis of compound Y.

Reagents/Actions Taken Observations
cis-MoO2(SCNEt2)2 + acetone honey brown

Filtration

Filtrate 1 honey brown solution

Residue 1 yellow brown solute

Filtrate + 12M HCl yellow-green solution

After swirling apple green solution

After standing in ice bath apple green solution with yellow solids forming

Filtration

Filtrate 2 apple green solution

Residue 2 bright yellow solid

After washing with acetone bright yellow solid

Product bright yellow solid

 Characterization was done by using Infrared and NMR spectroscopy. These were used for
structure elucidation. Theoretical value of the peaks found in the IR spectroscopy graph were
given and it was summarized in Table 4.6. Each peak was analyzed for specific stretches that
could possibly characterize the oxomolybdenum product that was synthesized in the experiment.
NMR spectroscopy, 1
H NMR spectroscopy determine the C – H attachements in the
oxomolybdenum compounds that were synthesized. Table 4.7 summarizes the chemical shifts
found in the 1H NMR spectroscopy data that was given.

Table 4.6. Infrared spectroscopy analysis of cis-MoO2(S2CNEt2)2, P, R, and Y.

Peak assignment
Compound Assignment
(cm-1)
1500 C-N stretch
900 Symmetric O=Mo=O vibration
cis-MoO2(S2CNEt2)2
880 Asymmetric O=Mo=O vibration
480 Mo-S vibration
1500 s C-N stretch
1440 s C-N stretch
Purple compound 1280 m N-R stretch
(P) 1010 w C-S stretch
940 s Mo=O stretch
420 w Mo-S stretch
1520 s C-N stretch
1440 m N-R stretch
Red compound
1280 m N-R stretch
(R)
1000 w C-S stretch
960 s Mo=O vibration
1540 s C-N stretch
1290 m N-R stretch
Yellow compound
1000 w C-S stretch
(Y)
950 m Mo=O vibration
580 w Mo-S vibration

Table 4.7. H1NMR analysis of cis – MoO2(S2CNEt2)2, P, R, and Y.

Compound δ, ppm Multiplicity Assignment # of H

1.25 Triplet -CH3 12

cis-MoO2(S2CNEt2)2
3.80 Quartet -CH2- 8
P - - - -
1.38 Triplet -CH3 12
R 3.87 Multiplet -CH2-*
8
3.93 Multiplet -CH2-*
1.42 Triplet -CH3 12
Y
3.90 Multiplet -CH2-* 8
*diasteriomers
 For cis-MoO2(S2CNEt2)2, the IR spectrum of the shows prominent peaks at 1500, 900, 880,
and 480 cm-1 that corresponds to (C-N) stretching, symmetric and asymmetric vibrations of the
(O-Mo-O) bridge, and (Mo-S) stretching, respectively. The NMR spectrum of MoO2(S2CNEt2)2
shows a triplet and a quartet at around δ 1.25 and δ 3.80, which indicates the presence of 4 –
CH3 and 4 –CH2– giving a total of 20 H atoms in the molecule. These data agree with the formula
for the intermediate product, cis-MoO2(S2CNEt2)2 (Shriner et al., 1997). Thus, the structure of cis-
MoO2(S2CNEt2)2 and trans-MoO2(S2CNEt2)2 are shown in Figure 4.3.

Figure 4.3. Structures of (a) cis-MoO2(S2CNEt2)2 and (b) trans-MoO2(S2CNEt2)2.

The formation of the cis isomer is more favored due to the Mo-O orbital interactions that would
stabilize the structure. The Opy-Modyz and Opx-Modxz interactions of the cis-isomer helps in
stabilizing the pi bonds making it more stable. In addition, Opz-Modz2 interaction preserves the
integrity of the sigma bonds. On the other hand, the Opy-Modyz interaction of the trans-isomer
weakens the Mo-O bond (Meislerr et al., 2014).

Figure 4.4. The π- and σ-bonding interactions of the filled orbitals of the O2- with
empty d orbitals.

The purple (P), red (R) and yellow (Y) products were also provided with mass
spectroscopy data for the determination of the molecular formula of each compound. Table 4.8
shows the data given for the determination of the molecular formula of the purple (P), red (R)
and yellow (Y) products.

Table 4.8. MS analysis for cis – MoO2(S2CNEt2)2, P, R, and Y.

P R Y
m/Z = 832 m/Z = 410 m/Z = 480
Atom
# of # of
Mass, g Mass, g Mass, g # of Atoms
Atoms Atoms
C 28.75 20 29.34 10 24.95 10
H 4.85 40 5.00 20 4.26 20
N 6.65 4 6.90 2 5.75 2
S 30.85 8 31.25 4 26.54 4
Cl - - - - 14.86 2
Mo 23.0625 2 23.40 1 19.9875 1
O 5.835 3 4.11 1 3.6525 1
MF Mo2O3(S2CNEt2)4 MoO(S2CNEt2)2 MoOCl2(S2CNEt2)2

For the purple compound, the IR spectrum shows an intense peak at 1500 cm-1 (C-N
stretching), a moderately strong peak at 940 cm-1 (Mo=O stretching) and a medium to weak but
sharp peak at 760 cm-1 (vibrations of the Mo-O-Mo bridge). The last peak confirms the presence
of the two Mo atoms in compound P. Furthermore, the mass spectral data for compound P was
also used to deduce its molecular formula. Given the percent by mass of the constituent elements
and m/z = 832, the number of the different atoms per mole of the unknown complex was
calculated obtaining the formula to be Mo2O3(S2CNEt2)4 (Shriner et al., 1997).

N
N
S
O S
S Mo
S O S
Mo S
S O
S
N

Figure 4.5. Structure of compound P, Mo2O3(S2CNEt2)4.

For the red compound, the IR spectroscopic data give two relevant peaks, 1520 and 960
cm-1. The 1520 peak corresponds to the C-N stretch, and the 960 peak corresponds to the Mo=O
group. Only one peak was observed at the 960 region which means that there is only one Mo=O
bond. Meanwhile, the NMR spectrum of compound R shows a triplet and a multiplet at about δ
1.38, δ 3.87 and δ 3.93 which corresponds to 4 –CH3 and 4 –CH2– like that of the intermediate
product giving a total of 20 H atoms in the molecule. Furthermore, the mass spectral data show
that the molecular mass of compound R is 410 g/mol (m/z=410). Calculation of the number of
the different atoms composing compound R gives the molecular formula MoO(S2CNEt2)2. The
structure of compound R using the spectroscopic analyses was deduced to be as shown below
(Shriner et al., 1997).

S S
N Mo N
S S
Figur 4.6. Structure of compound R, MoO(S2CNEt2)2.

For the yellow compound, the IR spectra gave two relevant peaks at 1540 cm-1 (C-N
stretch) and 950cm-1 (Mo=O stretch). Meanwhile, the NMR spectrum of compound R showed a
triplet and a multiplet at about δ 1.42 and δ 3.90 corresponding to 4 –CH3 and 4 –CH2–. Mass
spectral data show that the molecular mass of compound Y is 480 g/mol (m/z=480). Calculation
of the number of the different atoms composing compound Y gives the molecular formula
MoOCl2(S2CNEt2)2. It is heavier than compound R due to the presence of Cl atoms. The yellow
compound can have three isomers (Shriner et al., 1997). These three isomers are the following:

S S
N Mo N
S S
Cl Cl Isomer I
O

S Cl
N Mo
S S
Cl S

Isomer II
 O

S S
N Mo
S Cl
Cl S
N

Isomer III

Figure 4.7. Isomers of compound Y.

Among the three isomers, Isomer I is the most favored due to the least degree of steric
hindrance between Cl and O atoms. Its pentagonal bipyramidal geometry also gives the most
stable state wherein the two Cl and one O atoms are in mer position lying in the same plane, and
the dithiocarbamato ligands are in axial positions (Meislerr et al., 2014).
Finally, the last part of the experiment was the study of the oxygen transfer reactions.
The intermediate and compound R were used. First, a pinch of cis – MoO2(S2CNEt2)2 and
compound R were dissolved separately in dichloromethane. They were then mixed and then
observed. Initially the dissolution of cis – MoO2(S2CNEt2)2 in dichloromethane led to the formation
of a yellow solution while the dissolution of compound R in dichloromethane led to the formation
of a cherry red solution. Upon mixing, the resulting solution turned dark purple. The reaction that
have occurred in this oxygen transfer reaction is shown below below (Dirand, Ricard and Weiss,
1976). This reaction is a nucleophilic comproportionation reaction.
cis-MoVIO2(S2CNEt2)2 + MoIVO(S2CNEt2)2 Mo2VO3(S2CNEt2)4 (Eqn. 4.4)

Next, the red product in dichloromethane was exposed in air. In this oxygen transfer
reaction, it was observed that there was a formation of a red violet solution. The color of the
solution that was formed should be purple due to the formation of the purple product or the
intermediate, cis – MoO2(S2CNEt2)2 as shown in the following reactions below (Dirand, Ricard and
Weiss, 1976). This reaction is also a nucleophilic oxo transfer.

2 Mo(IV)O(S2CNEt2)2 + ½ O2 Mo2(V)O3(S2CNEt2)4 (Eqn. 4.5)

2Mo(IV)O(S2CNEt2)2 +½ O2 Mo(VI)O2(S2CNEt2)2 (Eqn. 4.6)

On the other hand, the last oxygen transfer reaction was the reaction of the red product with
hydrogen peroxide in excess triphenylphosphine. The red product was first dissolved in
dichloromethane before the hydrogen peroxide was added. This solution was observed to be
cherry red. After this, excess triphenylphosphine was added to the test tube, and the solution
became wine red. The first step produced based on this reaction is

Mo(IV)O(S2CNEt2)2 + H2O2 Mo(VI)O2(S2CNEt2)2 + H2O (Eqn. 4.7)

This reaction is a primary nucleophilic reaction. After that, the addition of PPh3 should result to
the formation of compound P based on the following reaction:
2Mo(VI)O2(S2CNEt2)2 + PPh3 Mo(IV)O3(S2CNEt2)4 + OPPh3 (Eqn. 4.8)
Meanwhile, this reaction is a secondary nucleophilic reaction which involves the oxidation of the
substrate with accompanying change on the oxidation state of both the metal and the ligand.
Then, the addition of excess PPh3 results to the formation of the R compound below (Dirand,
Ricard and Weiss, 1976).

Mo(VI)O2(S2CNEt2)2 + PPh3 (excess) Mo(IV)O(S2CNEt2)2 + OPPh3 (Eqn. 4.9)

For an oxo ligand transfer to occur, the oxygen atom donor should contain a metal center
with a high oxidation number. This reaction is intensified by a strongly oxidizing metal center, a
weak M=O bond, and an oxygen atom acceptor which forms relatively strong bond with oxygen
by increasing its valency (Holm, 1987). Table 4.10 shows the observation for the oxygen transfer
reactions.

Table 4.10. Observations for the oxygen transfer chemistry.

Test tube Reagents/ Action Taken Observations
cis – MoO2(S2CNEt2)2+ CH2Cl2 + R
1 Dark violet to purple solution
R+ CH2Cl2 exposed in air
2 Red violet solution
R+ CH2Cl2 + H2O2
3 Wine red solution
+excess PPh3
 II. Summary and Conclusion

In this exercise, cis – MoO2(S2CNEt2)2 as an intermediate for the preparation of

oxomolybdenum complexes was synthesized. The N,N-dithiocarbamate ligand was prepared in
situ and eventually added with the sodium molybdate(VI) dihydrate. This was followed by
dropwise addition of HCl with vigorous agitation. Vigorous agitation allows the regulation of pH
in the solution avoiding the formation of side products. The brown cis – MoO2(S2CNEt2)2 was then
isolated and washed. The cis – isomer predominates in the reaction since at this conformation, σ
and π interactions are more stable due to greater overlap in the filled p orbital of the oxo ligand
and the empty d orbital of molybdenum. Using this product, three complexes were synthesized
further namely compound P, compound R and compound Y. The structures of the intermediate
as well as compounds P, R and Y were elucidated using their IR, NMR and MS spectra. Oxygen
transfer experiments showed that for oxo ligands to transfer there should be a strongly oxidizing
metal center, a weak M=O bond, and an oxygen atom acceptor which forms relatively strong
bond with oxygen by increasing its valency.

III. References

Arzoumanian, H. 1998. Molybdenum-oxo chemistry in various aspects of oxygen atom transfer

processes. Coordination Chemistry Reviews. Vol. 178 pp. 1901-1920.

Holm, R. H. 1987. Metal-centered oxygen atom transfer reactions. Chem. Rev., 87 (6), pp
1401–1449

Miessler, G.L., and D. A. Tarr. 2014. Inorganic Chemistry, 5th ed. USA: Pearson Education, Inc.
pp. 437 – 450

Shriner, R.L., Hermann, C.K.F Morrill, T.C., Curtin, D.Y., and Fuson, R.C. The Systematic
Identification of Organic Compounds. New York: Pearson Education, Inc.
 IV. Sample Calculations

Percentage Yield
Compound P

Experimental Yield
% Yield   100%
Theoretical Yield
0.1308 g
  100%
0.1668 g
% Yield  57.02178%

Compound R

Experimental Yield
% Yield   100%
Theoretical Yield
0.2599 g
  100%
0.328
% Yield  80.0%

Compound Y

Experimental Yield
% Yield   100%
Theoretical Yield
0.0105
  100%
0.1919845
% Yield  5.47%