Name: Alvarez, Mark Louie Date Performed: September 28, 2017

Groupmate: Bugtong, Jerome Date Submitted: October 12, 2017

Group No.: 2

Exercise 4
Oxomolybdenum Chemistry

I. Results and Discussion

The experiment aimed to synthesize the complex cis-MoO2(S2CNEt2), which was then
utilized as a reactant to produce other oxomolybdenum complexes containing the N,N-
diethyldithiocarbamate ligand. Moreover, the chemical and spectroscopic properties of the
complexes were studies through test tube reactions, IR spectroscopy, 1H-NMR and mass
spectrometry.

Molybdenum is an element with an extremely rich and interesting chemistry and very
versatile applications in many different fields of human activity. Molybdenum found its varied use
in metallurgical applications. Because of its anti-wear properties, molybdenum compounds
became recognizable for use as lubricants particularly in extreme or hostile environmental
situations. Forms of molybdenum as molybdates are white and non-toxic, therefore they are used
as pigments due to the former and as efficient corrosion inhibitors and smoke suppressants as a
result of the latter. Compounds of molybdenum that show catalytic property have been studied
for their contribution to the liquefaction of coal, adding to their numerous applications as
catalysts. The breakthrough for molybdenum in the industrial field was in 1983, when Henri
Moissan prepared pure molybdenum by heating the impure metal in an electric furnace in a CO2
atmosphere (Braithwaite and Haber, 1994).

The interesting chemistry of molybdenum does not end in its multiple applications but
continues on its versatile physio-chemical properties which makes both the solution and solid
state chemistry very complex and interesting. Its oxidation states from II to VI and coordination
numbers from 4 to 6 give molybdenum varied stereochemistry and the ability to form compounds
with most inorganic and organic ligands and bi- and polynuclear compounds containing multiple
Mo-Mo bonds and/or bridging ligands (Braithwaite and Haber, 1994).

Among the classes of molybdenum compounds in the solid state, the most studied are the
oxides, sulfides and halides. The principal ore of molybdenum is molybdenite, which in its purified
form is MoS2. The word molybdenum originated from the Greek term molibdos, which was
originally associated with describing both lead and graphite centuries before molybdenum was
discovered. This confusion may have arisen from the lubricating properties of the concerned
materials (Braithwaite and Haber, 1994).

Concentration of molybdenum in the environment is high, most especially in sea water,

compared to other transition metals. In nature, molybdenum is usually involved in three very
different reaction classes. First, molybdenum complexes can undergo substitution reactions,
wherein addition of the incoming ligands occur in an expanded coordination sphere as such
1|Ex e r cise 4
Oxomolybdenum Chemistry
reaction for the metal proceed with an intermediate of a higher coordination number. In
comparison with organic chemistry, the pathway of substitution reactions for Mo-compounds is
analogous to that of the SN2 mechanism. An example of this reaction is given below.

Scheme 4.1. Substitution reaction of a molybdenum complex.

Another reaction involving molybdenum centers is electron transfer, which is observed in the
molybdenum blues and bronzes. One-electron redox reactions of Mo-complexes are very rapid
and are requiring of only a slight rearrangement of the coordination sphere. Lastly, the reaction
governing the syntheses in the experiment is atom transfer, which is illustrated by the reaction
below.

(4.1)

Atom transfer reactions may be solvent-assisted and not be simple reactions of MoO42-, that is.
The species are always in relatively fast equilibrium with higher coordination spheres (Frausto da
Silva and Williams, 2001).

Oxygen atom transfer (OAT) reactions, as shown in the reaction in equation 4.12 involve
a formal gain or loss of an oxygen atom or an oxidation-reduction.

(4.2)

In this reaction species AO, the oxygen donor, is reduced while A, the oxygen acceptor, is
oxidized, with the result that the atom transferred is maintained as oxide in reactant and product.
Oxygen atom transfer is a frequent reaction type in inorganic chemistry, particularly with main-
group compounds, but is not always recognized as a mechanism for reactions proceeding this
way (Holm, 1987).

The main species involved in such reactions is the oxo group, referring to oxide (O2-). In
coordination chemistry, the oxygen atom is bound only to one or more metal centers and it can
either be a terminal ligand or a bridging atom (Nugent, 1988).

Figure 4.1. a) Doubly bridging and b) terminal oxo ligands.

2|Ex e r cise 4
Oxomolybdenum Chemistry
The oxo ligand has the capability to stabilize high-valent metal centers by both - and -
interactions and is susceptible to both nucleophilic and electrophilic attack. Nucleophilic reactions
involving oxygen transfer cause the change in the oxidation state of the metal. As an illustration,
the nucleophilic attack by phosphine on a dioxo-Mo(VI) center leads to both an oxygen atom
transfer and a reduction of the molybdenum ion and oxidation of phosphorus in the reacting
phosphine:

(4.3)

Another reaction illustrating nucleophilic attack is that of oxygen atom donors (oxides, peroxides
and dioxygen) containing sulfur and nitrogen. These species can oxidize oxo-Mo(IV) complexes
to produce Mo(VI) species according to the reaction below.

(4.4)

On the other hand, electrophilic reactions involving oxomolybdenum complexes do not induce a
change in the oxidation state of the metal ion, and are facilitated by simple protonation. An
example is shown as follows.

(4.5)

If no other ligands are present, protonation is succeeded by condensation and polyoxomolybdate

formation. In the presence of other ligands, selective replacement of the oxo ligands may be
promoted by protonation. Aside from nucleophilic and electrophilic reactions, another prevalent
reaction in oxomolybdenum chemistry is the comproprotionation reactions shown in equation 4.6
(Young, 1995).

(4.6)

In a comproportionation reaction, an element in different oxidation states in different compounds

is converted to the same oxidation state (Mazumdar, 2008).

Oxygen atom transfer or oxo-transfer reactions can be distinguished in two types

primary and secondary. Primary oxo transfer requires that reactants XO/X are oxygen atom
donors/acceptors, the oxidation/reduction of atom M of positive oxidation state z/z+2 results from
atom transfer only and transferable or transferred oxygen is oxidic and is directly bound in a
terminal or bridging to M. The general equation for this type of reaction is given by:

(4.7)

The number of ligands, n, does not need to be constant in both reactant and product. Moreover,
XO in the reverse reaction is not necessarily uncoordinated to M. In most cases, the final product
of primary oxo transfer reactions is a binuclear -oxo species in which the oxidation state of M
has been increased by one unit. Such species form favorably, in general, by the forward, often
irreversible reaction shown in equation 4.8 when it is faster than the reaction given in equation
3|Ex e r cise 4
Oxomolybdenum Chemistry
4.8. Taking the overall reaction, the resulting reaction shown in equation 9 depicts a common
stoichiometry in oxo transfer processes.

(4.8)

(4.9)

On the other hand, secondary oxo transfer reactions can be identified in two reactions, one which
causes as internal redox reaction and one in which both metal and ligand are reduced due to
substrate oxidation. Equation 10 portrays the former reaction, wherein the coordination of ligand
L causes the internal redox reaction resulting in formation of ligand oxide LO which may or may
not dissociate from M.

(4.10)

Equation 11 depicts the latter reaction and is given by:

(4.11)

These two secondary reactions are related in such a way that a second reactant causes an internal
electron rearrangement in the first. Reaction 4.11 is different from reaction 4.10 since the transfer
is ligand-centered or no oxo-metal group is involved in the oxo transfer process (Holm, 1987).

A common ground for primary and secondary oxo transfer is that both of these reactions
are mediated by the metal, whose oxidation state is changed in the process. A difference is that
primary reactions are exclusively metal-centered by virtue of the foregoing requirements. Primary
reactions, wherein M is a transition metal, are of larger number and are currently in greater
interest and activity compared to those involving nonmetals. Secondary reactions, on the
contrary, are of substantially less frequent occurrence (Holm, 1987).

In reactions involving oxygen atom transfer, the oxidation of the metal and the reduction
of the substrate are enhanced by a strongly reducing metal center, a strong M-O bond, and an
oxygen atom donor with a relatively weak X-O bond. Given that the species X is a transition metal,
the oxygen atom donor X-O should have a capability to stabilize high valent complexes and a
metal center at high oxidation state. For the opposite reaction, the contrast of each requirement
is required. In the tabular figure shown in Figure 4.2, the major reagents that have been used in
oxo transfer are depicted.

4|Ex e r cise 4
Oxomolybdenum Chemistry
 Figure 4.2. Tabular illustration of principal oxo transfer reagents.

In contrast, oxygen atom acceptors should be able to extend their valency so that the incoming
electron pair from the oxygen can be accommodated. Tertiary phosphines, whose basicities or
nuceophilicities usually increase with the number of alkyl groups, are the most common oxygen
atom acceptors. Among the tertiary phosphines, triphenylphosphine is the most frequently
employed acceptor and suffices for a large number of reactions (Holm, 1987).

Molybdenum lies at the epicenter of oxo transfer chemistry. The transition element has
more oxo compounds prepared and characterized, more oxo transfer reactions are known, and
more catalytic systems based on these reactions have been devised than for any other element.
Furthermore, molybdenum forms an extensive set of isopoly- and heteropolyanions.
Oxomolybdenum(VI) anions are responsible for the aqueous solubility of the element, which in
sea water is the highest among the transition elements. Also, molybdenum serves as cofactors in
two groups of enzymes implicated in oxo transfer catalysis (Holm, 1987).

In stressing the variety of oxomolybdenum complexes, some of these compounds were

synthesized in the experiment. Initially, cis-MoO2(S2CNEt2)2 or cis-bis(N,N-
diethyldithiocarbamato)dioxomolybdenum(VI) was prepared according to the steps shown in
Table 4.1, which also contains the summary of observations in each step.

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Oxomolybdenum Chemistry
 Table 4.1. Observations on the synthesis of cis-MoO2(S2CNEt2)2.
Reagents/Actions Taken Observations
NaOH + distilled H2O clear colorless solution
+ diethylamine clear colorless solution
+ CS2 formation of globular solids
After swirling for 10 minutes yellow solution
+ sodium molybdate(VI) dihydrate yellow solution
+ conc. HCl formation of brown solids
Filtration ---
Filtrate green lliquid
Residue yellow to light brown precipitate
Washing of residue w/ distilled H2O yellow to light brown precipitate
Washing of residue w/ ethanol yellow to light brown precipitate
Dried residue yellow to light brown precipitate
cis-MoO2(S2CNEt2)2 yellow to light brown precipitate

As observed in Table 4.1, the first step done was the mixing of NaOH, distilled water, diethylamine
and CS2 in order to produce the ligand S2CNEt2- in situ. The preparation was done as such since
the ligand easily undergoes decomposition, and thus cannot be isolated separately. S2CNEt2- can
be synthesized easily because the dithiocarbamato ligand is kinetically stable; however, it is not
thermodynamically stable so it can immediately bind to the central metal upon introduction of the
molybdenum ion. The mixture was then swirled for 10 minutes. The reaction that occurred during
this step is shown as follows.

(4.12)

The source of Mo6+ ion, sodium molybdate(VI) dihydrate was then added to the solution.
Successively, concentrated HCl in water was added dropwise to the mixture over a period of 15
minutes. Vigorous stirring during the addition was done to prevent the reduction of Mo6+ to Mo5+
by controlling the pH of the solution. This prevents the possible occurrence of the following side
reactions:

(4.13)

(4.14)

The reaction involved in this step is given by equation 4.15 below.

(4.15)

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Oxomolybdenum Chemistry
The product was isolated form the mixture through filtration using sintered funnel. The isolated
residue was washed with distilled water and ethanol in order to remove impurities. The final
appearance of the synthesized cis-MoO2(S2CNEt2)2 was yellow to light brown in color. The weight
of the product was then taken and was compared with the theoretical yield in order to obtain a
percentage yield. Summary of data involving the percentage yield of the product is depicted in
Table 4.2.

Table 4.2. Data on the percentage yield of cis MoO2(S2CNEt2)2.

Parameter Value
Mass of Na2MoO4 used 0.5779
Mass of watchglass + filter paper + product, g 35.9576
Mass of watchglass + filter paper, g 35.4214
Mass of product, g 0.5362
Theoretical yield of product, g 1.01386
Percentage yield, % 52.88698637

As shown in Table 4.2, the mass of the desired product was 0.5362 g. In comparison to
the theoretical yield of 1.01386 g, a percentage yield of 52.88698637% was recorded. The
inadequacy in the amount of the product synthesized may be majorly affected by the inability to
cover the flask with a watchglass during swirling of solution after addition of CS2. The presence
of oxygen in the air may have caused the oxidation of cis-MoO2(S2CNEt2)2, thus causing the
lowering the yield of the product. Moreover, the synthesis of the trans- product, insufficient
swirling of reaction mixture and loss of solids during filtration were also factors in the decreased
amount of the product.

The next set of oxomolybdenum products resulted from the reaction of the synthesized
product, cis- MoO2(S2CNEt2)2, with specific reagents to produce the target compounds. The
spectroscopic properties of the oxomolybdenum products were then determined using IR, 1H-
NMR and mass spectroscopy. The spectral data given for each complex allowed for the elucidation
of structure and calculation of molecular mass of the complexes.

The first species synthesized was the purple (P) compound. The steps involved in the
preparation, as well as the observations, are summarized in the following table.

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Oxomolybdenum Chemistry
Table 4.3. Observations on the synthesis of compound P.
Reagents/Actions Taken Observations
cis-MoO2(S2CNEt2)2 + dichloromethane Yellow-brown mixture
Filtration 1 ---
Filtrate 1 Burgundy solution
Residue 1 Red-purple solids
Filtrate +PPh3 Black solution
Swirl and stand for 15min Dark purple mixture
Filtration 2 ---
Filtrate 2 Light purple solution
Residue 2 Black crystalline solid
Washing of residue with methanol Black crystalline solid
Drying of residue Black crystalline solid
Dried product P Dark purple crystalline solid

According to Table 4.3, the first step done was the mixing of dichloromethane and the solid cis-
MoO2(S2CNEt2)2, giving a yellow-brown mixture. This mixture was then filtrated, keeping the
burgundy filtrate, which was treated with triphenylphosphine (PPh3) dissolved in methanol from
which it was soluble into. Afterwards, the mixture was swirled for a few seconds and was allowed
to stand for 15 minutes in order for the reaction to proceed. The resulting mixture was filtrated,
giving a light purple liquid as filtrate and black crystalline solids as residue. The residue was then
washed with methanol to remove unreacted cis-MoO2(S2CNEt2)2 and other adhering impurities,
The final form of compound P appeared as dark purple crystalline solids.

The results have shown that compound P was actually green in color and would only
appear as purple when scratched or streaked in a piece of white paper. This property of compound
P is known as tribochromism, which is exhibited when crystalline compounds give a more highly
colored sate when they are ground. If the compounds crystallize in a metastable state then the
color change is irreversible, as exemplified by the case of fulgide shown in Figure 4.3.

Figure 4.3. Tribochromic configurations of fulgide.

The folded metastable form is bright yellow in its crystalline state, but turns to a dark-red color
on grinding due t the formation of the stable twisted form. Tribohcroism is also experienced in
certain spiropyrans, spirooxazines, and thioindigos (Bamfield and Hutchings, 2010).

8|Ex e r cise 4
Oxomolybdenum Chemistry
 The next complex prepared was the red (R) compound. The summary of steps and the
corresponding observations is shown in Table 4.4.

Table 4.4. Observation on the synthesis of compound R.

Reagents/Actions Taken Observations
yellow brown solid and
cis-MoO2(S2CNEt2)2 + PPh3
white solid pellet mixture
+ 1,2-dichloroethane dark violet mixture
During reflux for 15 minutes mixture became red violet in color
After reflux red violet solution
+ cold ethanol red violet mixture
Filtration ---
Filtrate light purple liquid
Residue red violet solids
Washing of residue with ethanol red violet solids
Washing of residue with diethyl ether red violet solids
Dried product R red solids

From the quantitative data depicted in Table 4.4, the first step involving the mixing of cis-
MoO2(S2CNEt2)2 and PPh3 in dichloroethane resulted to a dark violet mixture. As reflux was
employed, the mixture slowly became red violet in color. The same color was retained after reflux
and addition of cold ethanol. The refluxed mixture was then filtrated, giving a light purple liquid
as filtrate and red violet solids as residue. The solids were then washed with ethanol and diethyl
ether to eliminate impurities, most especially the starting oxomolybdenum reagent. The final form
of compound R appeared as red solids.

The last oxomolybdenum compound synthesized was the yellow (Y) compound. The
method and observations in the preparation are shown in Table 4.5.

Table 4.5. Observations on the synthesis of compound Y.

Reagents/Actions Taken Observations
cis-MoO2(SCNEt2)2 + acetone red-brown mixture
Filtration 1 ---
Filtrate 1 yellow liquid
Residue 1 brown solids
Filtrate 1 + 12 M HCl yellow mixture
After swirling yellow mixture
After standing in ice bath yellow green mixture
Filtration 2 ---
Filtrate 2 green liquid
Residue 2 yellow solids
After washing with acetone yellow solids
Dried product Y yellow solids

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Oxomolybdenum Chemistry
 The data in Table 4.5 implied that the initial appearance of the mixture was red-brown,
resulting from the combination of cis-MoO2(SCNEt2)2 and acetone. Filtration of the mixture gave
a yellow filtrate and brown solids as residue. The filtrate was treated with 12 M HCl, producing a
yellow mixture which was swirled and allowed to stand undisturbed in an ice bath. The latter
procedure changed the color of the mixture into yellow green. This was then filtrated to obtain a
green filtrate and yellow solids as residue. The solids were washed with acetone to remove
impurities, most especially unreacted cis-MoO2(SCNEt2)2. The yellow solids were then recorded
as the final form of compound Y.
To determine the reactions involved in the synthesis as well as the percentage yield of
each compound, the structure and molecular weights of the products were assessed and identified
using different spectroscopic techniques. Infrared (IR) spectroscopy is a technique under
vibrational spectroscopy, and is useful for providing characteristic fundamental vibrations that are
employed for the elucidation of molecular structure (mid-IR spectroscopy) and for measuring the
broad overtone and combination bands of some of the fundamental vibrations, employed for
rapid, accurate quantitation (near-IR spectroscopy). IR spectroscopy measures transitions
between molecular vibrational energy levels as a result of absorption of mid-IR radiation. This
interaction between light and matter is a resonance condition involving the electric-dipole
mediated transition between vibrational energy levels. IR vibrational bands are characterized by
their frequency (energy), intensity (polar character or polarizability), and band shape
(environment of bonds). The vibrational energy levels, hence the IR spectrum, are unique to each
molecule. The frequencies of these molecular vibrations depend on the masses of the atoms,
their geometric arrangement, and the strength of chemical bonds. The spectra provide
information on molecular structure, dynamics, and environment (Larkin, 2011).
Nuclear magnetic resonance (NMR) spectroscopy lays its foundation on the discovery of
physicist P. Zeeman that the nuclei of certain atoms behave strangely when subjected to a strong
external magnetic field. Fifty years later, F. Bloch and E. Purcell created the first crude NMR
spectrometer as an application of the nuclear Zeeman effect. From these two breakthroughs,
NMR spectroscopy has developed into a technique that allows molecular structure elucidation by
measuring the interaction of an oscillating radio-frequency electromagnetic field with a collection
of nuclei immersed in a strong external magnetic field. These nuclei are parts of atoms that, in
turn, are assembled into molecules. The results of the spectroscopy are shown in an NMR
spectrum, which provide information regarding molecular structure and dynamics two
characteristics of species that are difficult to be known using any other method (Macomber,
1998).
The information in Tables 4.6 summarizes the peaks and the corresponding band
assignments for each compound, allowing for the identification of functional groups and distinct
bonds.

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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

Moreover, the data in Table 4.7 indicate the information gathered from the NMR spectra
of each complex.
Table 4.7. H1NMR analysis of cis MoO2(S2CNEt2)2, P, R, and Y.
Compound , 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

The data shown in Table 4.6 for cis-MoO2(S2CNEt2)2 revealed that there were four
prominent peaks, in the IR spectra, at 1500, 900, 880 and 480 cm-1 corresponding to C-N
stretching, symmetric O=Mo=O vibration, asymmetric O=Mo=O vibration, and Mo-S stretching
respectively. Moreover, in Table 4.7, the 1H-NMR spectrum of the same complex showed the
presence of a triplet and a quartet at around 1.25 and 3.80, each corresponding to 4 -CH3

11 | E x e r c i s e 4
Oxomolybdenum Chemistry
and 4 -CH2- groups, capping the total hydrogen count to 20. Hence, the following structures for
cis- and trans- MoO2(S2CNEt2)2 were constructed.

(a) (b)

Figure 4.4. (a) cis- and (b) trans- MoO2(S2CNEt2)2.

The formation of the cis- isomer of MoO2(S2CNEt2)2 was favored over the trans product
because the interaction of the Opy-Modxy orbitals (py orbital in oxygen-dxy orbital in molybdenum)
of the former preserves the integrity of the -bonds rendering its stability over the latter. Aside
from this, the cis-isomer can also form two bonds using the Mo dz2 and O1pz orbitals, and the
Mo dx2- y2 and O2px atomic orbitals. On the contrary, the extent of interaction between the Opy-
Modyz orbitals (py orbital in oxygen and dyz orbital in Mo) of the trans configuration of the species
makes the Mo-O bond unstable by rendering it weak. The trans-isomer also has only one bond,
involving the Mo dz2 and O1pz orbitals.

Figure 4.5. The p bonding interactions of the filled

p orbitals of O2- with empty metal d orbitals.

Observing again the collated data from the IR spectra of compound P in Table 4.6, there
were 6 peaks recorded: strong or sharp (s) peaks at 1500 and 1440 cm-1 corresponding to C-N
stretching; moderately strong (m) peak at 1280 cm-1 corresponding to N-R stretch (where R is
the alkyl group/s attached to N) ; strong peak at 940 cm-1 but a weak peak at 1010 cm-1 both
corresponding to identical Mo=O fragments linked by an oxo bridge; and a weak (w) peak at 420
cm-1 for Mo-S stretching. No data from the 1H-NMR spectra of compound P were recorded.
Moreover, for compound R there were 5 observed peaks: strong peak at 1520 (C-N stretch);
moderately strong peaks at 1440 and 1280 cm-1 (N-R stretch); weak peak at 1000 cm-1 (C-S
stretch); and a sharp peak at 960 cm-1 (M=O vibration). 1H-NMR spectra of compound R revealed

12 | E x e r c i s e 4
Oxomolybdenum Chemistry
the presence of 20 hydrogen atoms: the presence of a triplet at 1.38 corresponding to 4 -CH3
groups and two multiplets at 3.87 and 3.93, signifying two diastereomers of the 4 -CH2- groups.
Lastly, the IR spectra of compound R gave 5 prominent peaks: sharp peak at 1540 cm-1
corresponding to C-N stretching; moderately strong peak at 1290 cm-1 indicating N-R stretching;
weak peak at 1000 cm-1 corresponding to C-S stretching; moderately strong peak at 950 cm-1
indicating Mo=O vibration; and weak peak at 580 cm-1 corresponding to Mo-S vibration. For the
1
H-NMR data of compound Y, there are a total of 20 hydrogen atoms in the complex: 12 -CH3
groups due to the presence of a triplet at around 1.42 and 4 -CH2- groups due to a multiplet at
around 3.90.

In determining the structures of compounds P, R and Y, their respective molecular masses

were obtained through a spectral data from mass spectrometry. Mass spectrometry is an
analytical method used to identify compounds based on the atomic constitution of their molecules
and their charge state. Samples or chemical species under study are ionized and the resulting
ions are sorted according to their mass-to-charge ratio. The technique applies for both analysis
of pure samples and complex mixtures. A mass spectrometer, whose block diagram is illustrated
in Figure 4.6, always have the following mechanical implements: a sample inlet to introduce the
compound that is analyzed, such as a gas chromatograph or a direct insertion probe; an ionization
source to produce ions from the sample; one or several mass analyzers to separate the various
ions; a detector to give a corresponding amount of the ions emerging from the last analyzer; and
a data processing system that provides data by generating a mass spectrum. In some other mass
spectrometers, the sample inlet and the ionization source or the mass analyzer and the detector
are combined (de Hoffman and Stroobant, 2007).

Figure 4.6. Basic diagram for a mass spectrometer with two analyzers
and feedback control carried out by a data system.

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 The number of moles of C, N, H, and S in each complex was calculated using the equation

(4.16)

where nx corresponds to the number of moles of element x and the obtained mass of atom is the
interpretation of the percentage values obtained in the mass spectrometer data given. The
number of atoms of each constituent element can then be computed using the equation

(4.17)

where m/z corresponds to the mass-to-charge ratio in units of g/mol obtained from the mass
spectrometry data while the mass of the compound was taken to be 100 g. The molecular formula
for these constituent atoms can then be determined, which can then be used to determine the
moles and number of atoms of Mo and O. The formula for finding the number of atoms of Mo
and O is given by

(4.18)

where the mass of element is calculated through stoichiometric computations relating the number
of moles of either Mo and O to the number of moles of the assembled formula including only C,
H, N, and S of the complex under study. The results of the calculations lead to the elucidation of
the molecular formula of each complex, which are reflected in Table 4.8.

Table 4.8. Mass spectroscopic analysis of compounds 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
Molecular
Mo2O3(S2CNEt2)4 MoO(S2CNEt2)2 MoOCl2(S2CNEt2)2
Formula

14 | E x e r c i s e 4
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 Adding into the previous data on IR and 1H-NMR spectroscopy of the compound P, as
evident in Table 4.8, the molecular formula deduced was Mo2O3(S2CNEt2)4 or -oxo-tetrakis(N,N-
diethyldithiocarbamato)dioxomolybdenum(V), which has the following structure.

Figure 4.7. Elucidated structure of compound P, Mo2O3(S2CNEt2)4.

On the other hand, the molecular formula obtained for compound R was MoO(S2CNEt2)2 or
bis(N,N-diethyldithiocarbamato)oxomolybdenum(IV) which has the following structure.

Figure 4.8. Elucidated structure of compound R, MoO(S2CNEt2)2.

For compound Y, the molecular formula deduced was MoOCl2(S2CNEt2)2 or dichlorobis(N,N-

diethyldithiocarbamato)oxomolybdenum(VI). This compound is heavier compared to the other
two due to the presence of two chlorine atoms. A special characteristic of compound Y is that it
has three isomers, which are all illustrated as follows.

(I)

15 | E x e r c i s e 4
Oxomolybdenum Chemistry
 (II) (III)

Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl2(S2CNEt2)2.

Among the three isomers of MoOCl2(S2CNEt2)2, the most favored structure for formation is isomer
I, which have a pentagonal bipyramidal geometry. The isomer has the least steric hindrance
between the two large S and Cl atoms since the dithiocarbamato ligands are in axial position.

The elucidation of structure and identification of molecular formula of the three complexes
P, R and Y paved the way for the recording of necessary reactions which occurred in the synthesis
as well as the corresponding percentage yield. For the synthesis of the purple compound P, the
use of dichloromethane to dissolve cis-MoO2(S2CNEt2)2 provides an environment for the reaction
to proceed, and through filtration the undissolved impurities were removed. The purpose of
methanol was to dissolve PPh3 so the latter can react with cis-MoO2(S2CNEt2)2. Treatment of the
filtrate with the PPh3 solution resulted to a nucleophilic type of oxo transfer reaction wherein the
oxidation state of Mo changed from VI to IV.

(4.16)

As seen in the reaction above, the molybdenum in the complex was reduced while phosphorus in
PPh3 was oxidized. Hence, PPh3 acted as the reducing agent and as an oxygen acceptor in the
reaction. Moreover, swirling and standing caused the following reaction to proceed:

(4.17)

Reaction 4.17 shows the condensation of the two reactants to produce the dark purple solid,
Mo2O3(S2CNEt2)4, which is a binuclear -oxo species. Also, the oxidation state of Mo decreased
by one unit (to V) with respect to the initial Mo-containing reactant. Hence, reactions 4.16 and
4.17 can both be regarded as primary oxo transfer reactions.

In the synthesis of the red compound R, the purpose of PPh3 was the same as that in the
preparation of compound P. PPh3 served as the oxygen acceptor and as a reducing agent causing
the reduction of Mo(VI) to Mo(IV). The solvent 1,2-dichloroethane provided an appropriate

16 | E x e r c i s e 4
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reacting medium for cis-MoO2(S2CNEt2) and PPh3, implying that it is unreactive to both the
reactants. Refluxing of the mixture was done to prevent air oxidation of compound R as it is being
formed since it is moderately air-sensitive. PPh3 was added in excess with respect to cis-
MoO2(S2CNEt2) because it would be oxidized in air first, thus preventing the occurrence of the air
oxidation of compound R. The reaction involved in the synthesis of compound R is given by:

(4.18)

The reaction is a nucleophilic type of oxo transfer since the oxidation state of Mo changed from
VI to IV. It is also a primary oxo transfer reaction because the reactants acted in each own way
as a oxygen atom donor and acceptor, and at the same time the difference in oxidation state of
Mo after the reaction is 2.

Finally, in the synthesis of the yellow compound Y, acetone was used as the solvent in
order to provide a medium wherein the starting materials can properly react and the target
compound can precipitate easily when formed. Hence, compound Y is and should not be soluble
in acetone. The initial filtration step was done to remove any impurities which may have been
incorporated in cis-MoO2(S2CNEt2). Concentrated HCl was the source of chloro ligands in the
preparation, and its addition promoted the electrophilic reaction for the formation of compound
Y as seen in the reaction below.

(4.19)

The oxo transfer reaction is electrophilic because the oxidation state of Mo remain the same after
the reaction and a simple protonation process occurred. An oxygen atom was transferred to HCl,
but at the same time the chloro ligand attached to the metal center. Unlike the previous synthesis,
the reaction did not utilize PPH3 as an oxygen acceptor. This was because the concentration of
HCl was high enough to facilitate an electrophilic reaction, thus no transferring of oxygen to PPh3
was needed.

Each of the complexes were weighed and the percentage yield for the syntheses were
accounted for. The following table summarizes the data involved in the calculaton of the
percentage yield of each colored oxomolybdenum complex.

Table 4.9. Data for the percentage yield of compounds P, R and Y.

Compound
P R Y
Mass of watchglass + filter
33.6330 44.6895 44.5125
paper + product, g
Mass of watchglass + filter
33.5003 44.4113 44.4998
paper, g
Mass of product, g 0.1327 0.2782 0.0127
Theoretical yield of product, g 0.3324089307 0.3192934921 0.1919895496
Percentage yield, % 39.92070842 87.12986857 6.614943378

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 As evidently seen in Table 4.9, the highest percentage yield of 87.12986857% was
obtained for compound R while the lowest percentage yield of 6.614943378% was recorded for
compound Y. For all preparations, decrease in yield may be accounted for by losses in residue
during filtration and transferring of filter paper into watchglass and insufficient drying, and
ultimately by the impurity of the prepared cis-MoO2(S2CNEt2)2. For the synthesis of compound P,
the low yield may be due to insufficient swirling and standing. In the case of compound Y, the
relatively very low yield can be traced to inadequate addition of HCl and swirling and to
disturbances in the reaction during standing in ice bath.

The final experimental procedure investigated the oxygen transfer chemistry of the synthesized
oxomolybdenum complexes, specifically cis-MoO2(S2CNEt2)2 and compound R, through test tube
reactions. The following table shows the observations recorded for each reaction.

Table 4.10. Observations on the test tube reactions for studying the oxygen transfer chemistry
of oxomolybdenum compounds.
Test tube Reagents/ Action Taken Observations
cis MoO2(S2CNEt2)2+ CH2Cl2 canary yellow solution
1 compound R + CH2Cl2 pink solution
Resulting Mixture dark red solution
cherry red solution to
2 compound R+ CH2Cl2 exposed in air
dark cherry red solution
compound R+ CH2Cl2 clear dark red liquid
3 + H2 O 2 yellow solution
+excess PPh3 light cherry red solution

The first reaction performed, as shown in Table 4.10, involved the dissolution of cis
MoO2(S2CNEt2)2 in dichloromethane, giving a canary yellow solution. The same was done for
compound R which resulted to a pink solution. The combination of the two solutions gave rise to
a dark red solution. The reaction involved for this test tube reaction is given as follows.

(4.20)

Supposedly, the comproportionation reaction given by reaction 4.20 should occur, giving a purple-
colored solution due to the formation of compound P. The reaction between the two starting
compounds produces a binuclear oxomolybdenum complex wherein O is the bridging ligand and
the oxidation state of Mo changed from VI and IV to V (Young, 1995).

The next reaction achieved was the exposure of compound R dissolved in CH2Cl2 to open
air. An initial cherry red solution shifted to dark cherry red after reaction with oxygen in the air.
However, the following reaction should have taken place:

(4.21)

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The resulting color of the solution should be yellow-brown, due to the formation of cis
MoO2(S2CNEt2)2, instead of dark cherry red. The oxo transfer reaction that occurred is
nucleophilic, wherein O2 in air served as the oxidizing agent causing the oxidation state of Mo to
change from IV to VI. Failure of this and the previous reaction may be due to the impurities
present in compound R, or in a more elaborate case, that the complex synthesized was not
actually the desired red compound.

The last reaction performed was the addition of two drops of hydrogen peroxide solution
to a solution of compound R in CH2Cl2 and addition of excess PPh3 to the resulting solution. From
a dark red solution, the color changed to yellow, and then to light cherry red after the respective
reactions. The reactions involved are presented as follows.

(4.22)

(4.23)

Reaction 4.22 is a nucleophilic reaction, wherein H2O2 acts as an oxidizing agent and as an oxo-
donor, causing the oxidation of MoIV to MoVI. The reaction yielded the yellow-brown cis
MoO2(S2CNEt2)2 as intermediate. Succeedingly, reaction 4.23 also proceeds in a nucleophilic oxo
transfer fashion, wherein PPh3 served as the reducing agent and oxo-acceptor, causing the
reduction of MoVI to MoIV. The initial red molybdenum complex, compound R (MoO(S2CNEt2)2),
was again produced in the reaction.

The 20th century utilization of molybdenum is widely given importance, especially that the
transition metal have numerous technological, metallurgical and chemical uses. It was not until
the 1930s when the biological importance of molybdenum was recognized, the event wherein Mo
was reported to have stimulatory effect on the process of biological nitrogen fixation. The
presence of molybdenum in the enzyme nitrogenase was fully appreciated by the early 1970s.
Through the crystallographic elucidation of nitrogenase structures, it was confirmed that
molybdenum is present in FeMoco, the iron-molybdenum cofactor, which is the central part of
the active site of nitrogenase. Not less than 50 years back, molybdenum was identified as the
xanthine oxidase factor as enzymes containing the metal can catalyze oxygen atom transfer
reactions. Other enzymes that can act as catalysts for such type of reactions include nitrate
reductase and sulfite oxidase. Since then, Mo has been discovered in a variety of enzymes. Each
enzyme contains a mononuclear Mo site with one or two unusual pterin-ene-dithiolate ligands
and, usually one or more oxo groups in the molybdenum coordination sphere. The molybdenum
center in these enzymes, coordinated by the special ligand family, is designated Moco or the
molybdenum cofactor. Figure 4.10 shows the essential features of the Moco family, with its pterin-
ene-dithiolate and other non-protein ligand(s) (Stiefel, 1997).

19 | E x e r c i s e 4
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 Figure 4.10. A general schematic representation of the
extended structure of the molybdenum sites in enzymes (Moco).

Molybdenum provides facile electron-transfer pathways for biochemical processes. The

stability of the Mo(VI) and Mo(IV) oxidation levels with an appropriate number of terminally bound
ligands allow the occurrence of such reactions. Moreover, the molybdenum sites with such
oxidation states can undergo oxygen-transfer reactions. The oxide ligand bridges the redox
partners, allowing the two-electron transfer to occur, and ends up bound to the oxidized reaction
partner. In the nitrogen cycle, where both nitrogenase and nitrate reductase are key operatives,
the preeminence of molybdenum in plant and microorganism metabolism is notable. Molybdenum
enzymes also play crucial roles in catalyzing reactions involved in the sulfur and carbon cycle.
Some of substrate reactions of molybdenum enzymes are shown in Figure 4.11.

Figure 4.11. Tabular illustration of stoichiometric formulations

for substrate reactions of molybdenum enzymes.
20 | E x e r c i s e 4
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 Nitrate reductases play key roles in the first step of biological nitrogen cycles i.e.,
assimilatory ammonification (to incorporate nitrogen into biomolecules) dentrification (to
generate energy for cellular function) and dissimilatory ammonification (to dissipate extra energy
by respiration). These enzymes catalyze the reduction of nitrate to nitrite in acidic conditions.
Among the three classes of nitrate reductases, membrane bound respiratory nitrate reductase
(Nar) catalyzes nitrate reduction, which is an important step of the dentrification in the anaerobic
respiratory pathways employed by a diverse group of bacteria and archaea. Molybdenum then
goes into picture by serving as a cofactor of Nar, and it is found in all microbes from which it was
isolated and belongs to the DMSO reductase family. Nar reduces nitrate to nitrate, causing the
change in oxidation state of Mo (or tungsten, W) from +IV to +VI, according to the following
reaction.

(4.24)

Molybdenum was found to be present in an active site of dissimilatory nitrate reductase, in which
it is bound by two metalopterin dithiolene ligands and a cysteine residue. An experimental study
on small model complexes demonstrates that nitrate reduction by primary oxo transfer is a
feasible reaction pathway, as seen in the figure below.

Figure 4.12. Schematic description of the proposed mechanism

for the nitrate reduction (M = Mo; Y = S-Cys).
(Mechanism was lifted from Hille, R. 1996. The mononuclear molybdenum enzymes. Chem.
Rev. 96(7):2757-2816)

Molybdenum basically coordinates the metalloprotein or some of its variants in mononuclear

enzymes. According to Figure 4.12, molybdenum acted as an oxygen acceptor from which initially
nitrate attaches and leaves with an oxygen group bound to the central metal (Habib and Hoffman,
2017).

21 | E x e r c i s e 4
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II. Summary and Conclusion

The experiment first employed the preparation of the oxomolybdenum complex, cis-
MoO2(S2CNEt2)2, through the use of reagents containing the metal center and the ligands. The N-
N-dithiocarbamate ligand was prepared in situ and was made to react with sodium molybdate(VI)
dihydrate. In order to promote the electrophilic reaction, dropwise addition of HCl with vigorous
agitation was employed. The rapid motion was made to regulate the pH of the solution to prevent
the formation of unwanted products. After the formation of solids, the mixture was filtered and
the residue was recovered and washed, with the cis-MoO2(S2CNEt2)2 appearing as yellow-brown
solids. The cis isomer of the compound was favored over the trans product because such
conformation preserves the integrity of the and bonds. An electrophilic oxo transfer reaction
has occurred since the oxidation state of molybdenum remains as +VI until the formation of the
product. The weight of the product was 0.5362 g, giving a low percentage yield of
52.88698637%.

The synthesized cis-MoO2(S2CNEt2)2 was then used as a reactant to synthesize three

unknown compounds (P, R and Y). Compound P (for purple) was prepared with dichloromethane
as the reaction solvent and PPh3 as the reducing agent, decreasing the oxidation state of Mo from
VI to IV. The final form of the product appears as dark purple, although it should have been
initially green, and would only assume such color if it is scratched as compound P exhibits
tribochromism. The reaction is a nucleophilic type of oxo-transfer due to the apparent change in
oxidation state of the metal center. Through the assessment of the provided IR, 1H-NMR and
mass spectroscopy data, compound P was found to be a binuclear -oxo species with a molecular
formula of Mo2O3(S2CNEt2)4. The synthesized compound P has a mass of 0.1327 g and a low
percent yield of 39.92070842%.

Compound R (for red) was synthesized by performing reflux on a mixture of cis-

MoO2(S2CNEt2)2 and PPh3, the latter compound added in excess and acted as a reducing agent
to diminish the oxidation state of Mo from VI to IV. The reflux process was done to prevent air
oxidation of compound R, which was moderately-air sensitive. The product, after filtration,
appeared as solids with red color. The reaction is nucleophilic similar to the previous synthesis.
From the provided data gathered from IR, 1H-NMR and mass spectroscopy, it was revealed that
compound R has a molecular formula of MoO(S2CNEt2)2. The prepared complex R has a weight
of 0.2782 g with a high percentage yield of 87.12986857%.

Finally, the preparation of compound Y (for yellow) was accomplished by employing

acetone as reaction medium and treating the filtrate after filtration with concentrated HCl to elicit
chloride ions as ligands and to promote electrophilic reaction for the formation of the desired
complex with cis-MoO2(S2CNEt2)2 as starting reagent. The final appearance of compound Y was
solid with yellow color. An electrophilic oxo transfer reaction occurred since the oxidation state of
molybdenum remain VI throughout the reaction. Through interpretation of IR, 1H-NMR and mass
spectroscopy data, the molecular formula of compound Y was found to be MoOCl2(S2CNEt2)2. The
synthesized compound Y recorded a mass of 0.0127 and a very low yield of 6.614943378%.

The final experimental part made use of cis-MoO2(S2CNEt2)2 and compound R in a series
of test tube reactions that allow for the manifestation of the chemistry of oxygen transfer. The
first reaction was initiated by mixing solutions of cis MoO2(S2CNEt2)2 and compound R in CH2Cl2
gave a dark red solution, which should have been dark violet due to the formation of the purple
22 | E x e r c i s e 4
Oxomolybdenum Chemistry
compound P. A comproportionation reaction has occurred due to the formation of a binuclear
oxomolybdenum complex with O as bridging ligand. The next reaction involved air oxidation of
compound R, resulting to a dark cherry red solution, which should have been yellow-brown due
to the production of the cis-oxomolybdenum complex. A nucleophilic oxo transfer reaction has
happened since O2 in the air served as oxidizing agent and as oxygen donor and the oxidation
state of Mo increased from IV to VI. Lastly, addition of a solution of H2O2 in a CH2Cl2 solution of
compound R resulted to a yellow solution indicating the formation of cis-MoO2(S2CNEt2)2.
Furthermore, excess PPh3 was added to this solution, transforming the color of the solution into
light cherry red, signaling the formation of compound R. The reaction is also nucleophilic due to
H2O2 acting as an oxidizing agent and oxo-donor and to the increase in oxidation state of Mo from
IV to VI.

For this experiment, it is recommended to employ the procedures more properly and
carefully or to modify the methods in order to increase the yield of the oxomolybdenum
complexes. Moreover, more test tube reactions may be employed to extend the knowledge on
the variety of simple reactions that oxomolybdenum compounds can undergo.

III. References

Bamfield, P. and Hutchings, M.G. 2010. Chromic Phenomena: Technological Applications of Colour
Chemistry, 2nd ed. United Kingdom: The Royal Society of Chemistry, p. 105.
Braithwaite, E.R. and Haber, J. 1994. Molybdenum: An Outline of its Chemistry and Uses. Studies
in Inorganic Chemistry, 19. Netherlands: Elsevier Science B.V.
de Hoffman, E. and Stroobant, V. 2007. Mass Spectrometry: Principles and Applications. England:
John Wiley & Sons Ltd, pp. 1, 4-5.
Frausto da Silva, J.J.R. and Williams, R.J.P. 2001. The biological chemistry of the elements: The
inorganic chemistry of life. England: OUP Oxford, p. 422.
Habib, U. and Hoffman, M. Effect of molybdenum and tungsten on the reduction of nitrate in
nitrate reductase, a DFT study. Chemistry Centrak Journal (2017) 11:35.
Holm, R.H. Metal-Centered Oxygen Atom Transfer Reactions. Chem. Rev. 1987, 87 1401-1449.
Larkin, P. 2011. Infrared and Raman Spectroscopy: Principles and Spectral Interpretation.
Amsterdam: Elsevier, pp. 1-3, pp. 27-31.
Macomber, R.S. 1998. A Complete Introduction to Modern NMR Spectroscopy. United States:
John Wiley & Sons, Inc., p. 1.
Mazumdar, M. 2008. Rudiments of Chemistry. India: Academic Publishers.
Nugent, W.A and Mayer, J.M. 1988. Metal-Ligand Multiple Bonds. New York: John Wiley & Sons.
Stiefel, E.I. Chemical keys to molybdenum enzymes. J. Chem. Soc., Dalton Trans., 1997, 3915-
3923.
Young, C.G. Oxomolybdenum Chemistry: An Experiment. J. Chem. Ed. 1995, 72:8, 751-653.

23 | E x e r c i s e 4
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Calculations

1. Molecular Formula
a. Purple Compound, P
i. Number of moles of C, N, H and S

ii. Number of C, N, H and S atoms

24 | E x e r c i s e 4
Oxomolybdenum Chemistry
iii. Mass of Mo and O

iv. Number of atoms of Mo and O

v. Molecular Formula
Mo2O3C20H40N4S8 or Mo2O3(S2CN(CH2CH3)2)4 or Mo2O3(S2CNEt2)4

25 | E x e r c i s e 4
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b. Red Compound, R
i. Number of moles of C, N, H and S

ii. Number of atoms of C, N, H and S

26 | E x e r c i s e 4
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iii. Mass of Mo and O

1 mole Mo 2 mole S 2 CN C 2 H 5 2
From the data S 4 C10 H 20 N 2 or S 4 C 2 N 2 C 4 H 10 2
S 2 x C x N x C 2 x H 5 x 2 S 22 C 2 N 2 C 22 H 52 2
x 2 moles S 2 CN C 2 H 5 2
moles Mo 1
1 moles Mo 1 moles P 95.94 g Mo
mass Mo 100 g P 23.4 g
1 moles P 410 g P 1 moles Mo
mass O 100 g m C m H m N m S m Mo
mass O 100 g 29.34 g 5.00 g 6.90 g 31.25 g 23.4 g 4.11g

iv. Number of atoms of Mo and O

v. Molecular Formula
MoOC10H20N2S4 or MoO(S2CN(CH2CH3)2)2 or MoO(S2CNEt2)2

27 | E x e r c i s e 4
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c. Yellow Compound, Y
i. Number of moles of C, N, H and S

ii. Number of atoms of C, N, H and S

480 g mol
C 2.07743547 moles 9.971690256 10
100g
480 g mol
H 4.226190476moles 20.28571428 20
100g
480 g mol
N 0.4104211278moles 1.970021413 2
100g
480 g mol
S 0.8275647022moles 3.972310571 4
100 g
480 g mol
Cl 0.4191819464moles 2.012073343 2
100 g

28 | E x e r c i s e 4
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 iii. Mass of Mo and O
1 mole Mo 2 mole S 2 CN C 2 H 5 2
From the data S 4 C10 H 20 N 2 or S 4 C 2 N 2 C 4 H 10 2
S 2 x C x N x C 2 x H 5 x 2 S 22 C 2 N 2 C 22 H 52 2
x 2 moles S 2 CN C 2 H 5 2
moles Mo 1
1 moles Mo 1 moles P 95.94 g Mo
mass Mo 100 g P 19.9875 g
1 moles P 480 g P 1 moles Mo
mass O 100 g m C m H m N m S m Cl m Mo
mass O 100 g 24.95 g 4.26 g 5.75 g 26.54 g 14.86 g 19.9875 g 3.6525 g
iv. Number of atoms of Mo and O

v. Molecular Formula
MoOC10H20N2S4Cl2 or MoOCl2(S2CN(CH2CH3)2)2 or MoOCl2(S2CNEt2)2

2. Percentage Yield

a. cis-MoO2(S2CNEt2)2

Experimental Yield
% Yield 100%
Theoretical Yield
0.5362 g
100%
1.01386 g
% Yield 52.88698637%

29 | E x e r c i s e 4
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b. Compound P

Experimental Yield
% Yield 100%
Theoretical Yield
0.1327 g
100%
0.3324089307 g
% Yield 39.92070842%

c. Compound R

Experimental Yield
% Yield 100%
Theoretical Yield
0.2782 g
100%
0.3192934921 g
% Yield 87.12986857%

d. Compound Y

Experimental Yield
% Yield 100%
Theoretical Yield
0.0127 g
100%
0.1919895496 g
% Yield 6.614943378%

30 | E x e r c i s e 4
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