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Name: Alvarez, Mark Louie Groupmate: Bugtong, Jerome Group No.: 2

Date Performed: September 28, 2017 Date Submitted: October 12, 2017

Exercise 4 Oxomolybdenum Chemistry

I. Results and Discussion

The experiment aimed to synthesize the complex cis-MoO 2 (S 2 CNEt 2 ), 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, 1 H-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 CO 2 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 MoS 2 . 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

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 S N 2 mechanism. An example of this reaction is given below.

reaction for the metal proceed with an intermediate of a higher coordination number. In comparison with

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.

reaction for the metal proceed with an intermediate of a higher coordination number. In comparison with

(4.1)

Atom transfer reactions may be solvent-assisted and not be simple reactions of MoO 4 2- , 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.

reaction for the metal proceed with an intermediate of a higher coordination number. In comparison with

(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 (O 2- ). 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).

reaction for the metal proceed with an intermediate of a higher coordination number. In comparison with

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

The oxo ligand has the capability to stabilize high-valent metal centers by both σ- and π- 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:

The oxo ligand has the capability to stabilize high-valent metal centers by both σ - and

(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.

The oxo ligand has the capability to stabilize high-valent metal centers by both σ - and

(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.

The oxo ligand has the capability to stabilize high-valent metal centers by both σ - and

(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).

The oxo ligand has the capability to stabilize high-valent metal centers by both σ - and

(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:

The oxo ligand has the capability to stabilize high-valent metal centers by both σ - and

(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 μ-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

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)
(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)

(4.10)

Equation 11 depicts the latter reaction and is given by:

(4.11)

(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.

Figure 4.2. Tabular illustration of principal oxo transfer reagents. In contrast, oxygen atom acceptors should be

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-MoO 2 (S 2 CNEt 2 ) 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.

Table 4.1. Observations on the synthesis of cis-MoO 2 (S 2 CNEt 2 ) 2 .

 

Observations

Reagents/Actions Taken NaOH + distilled H 2 O

clear colorless solution

+ diethylamine

clear colorless solution

+ CS 2

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 H 2 O

yellow to light brown precipitate

Washing of residue w/ ethanol

yellow to light brown precipitate

Dried residue

yellow to light brown precipitate

cis-MoO 2 (S 2 CNEt 2 ) 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 CS 2 in order to produce the ligand S 2 CNEt 2 - in situ. The preparation was done as such since the ligand easily undergoes decomposition, and thus cannot be isolated separately. S 2 CNEt 2 - 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.

Table 4.1. Observations on the synthesis of cis-MoO (S CNEt ) . Observations Reagents/Actions Taken NaOH

(4.12)

The source of Mo 6+ 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 Mo 6+ to Mo 5+ by controlling the pH of the solution. This prevents the possible occurrence of the following side reactions:

Table 4.1. Observations on the synthesis of cis-MoO (S CNEt ) . Observations Reagents/Actions Taken NaOH

(4.13)

(4.14)

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

Table 4.1. Observations on the synthesis of cis-MoO (S CNEt ) . Observations Reagents/Actions Taken NaOH

(4.15)

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-MoO 2 (S 2 CNEt 2 ) 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 –MoO 2 (S 2 CNEt 2 ) 2 . Parameter

Value

Mass of Na 2 MoO 4 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

 

1.01386

Theoretical yield of product, g 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 CS 2 . The presence of oxygen in the air may have caused the oxidation of cis-MoO 2 (S 2 CNEt 2 ) 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- MoO 2 (S 2 CNEt 2 ) 2 , with specific reagents to produce the target compounds. The spectroscopic properties of the oxomolybdenum products were then determined using IR, 1 H- 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.

Table 4.3. Observations on the synthesis of compound P.

 

Observations

Reagents/Actions Taken cis-MoO 2 (S 2 CNEt 2 ) 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- MoO 2 (S 2 CNEt 2 ) 2 , giving a yellow-brown mixture. This mixture was then filtrated, keeping the burgundy filtrate, which was treated with triphenylphosphine (PPh 3 ) 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-MoO 2 (S 2 CNEt 2 ) 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.

Table 4.3. Observations on the synthesis of compound P. Observations Reagents/Actions Taken cis -MoO (S CNEt

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).

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 cis-MoO 2 (S 2 CNEt 2 ) 2 + PPh 3

 

Observations

 

yellow brown solid and

+ 1,2-dichloroethane

white solid pellet mixture dark violet mixture

 

mixture became red violet in color

During reflux for 15 minutes After reflux

red violet solution

+ cold ethanol

red violet mixture

Filtration

---

Filtrate

 

Residue

light purple liquid red violet solids

Washing of residue with ethanol

red violet solids

 

red violet solids

Washing of residue with diethyl ether Dried product R

red solids

From the quantitative data depicted in Table 4.4, the first step involving the mixing of cis- MoO 2 (S 2 CNEt 2 ) 2 and PPh 3 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

 

red-brown mixture

cis-MoO 2 (SCNEt 2 ) 2 + acetone Filtration 1

---

Filtrate 1

yellow liquid

Residue 1

brown solids

Filtrate 1 + 12 M HCl

yellow mixture

After swirling

 
 

yellow mixture yellow green mixture

After standing in ice bath Filtration 2

---

Filtrate 2

green liquid

Residue 2

yellow solids

 

yellow solids

After washing with acetone Dried product Y

yellow solids

The data in Table 4.5 implied that the initial appearance of the mixture was red-brown, resulting from the combination of cis-MoO 2 (SCNEt 2 ) 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-MoO 2 (SCNEt 2 ) 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.

Table 4.6. Infrared spectroscopy analysis of cis-MoO 2 (S 2 CNEt 2 ) 2 , P, R, and Y. Peak assignment

Compound

(cm -1 )

Assignment

 

1500

C-N stretch

cis-MoO 2 (S 2 CNEt 2 ) 2

900

Symmetric O=Mo=O vibration

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

Red compound

(R)

1440

m

N-R stretch

1280

m

N-R stretch

1000

w

C-S stretch

 

960

s

Mo=O vibration

 

1540

s

C-N stretch

Yellow compound

(Y)

1290

m

N-R stretch

1000

w

C-S stretch

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. H 1 NMR analysis of cis – MoO 2 (S 2 CNEt 2 ) 2 , P, R, and Y.

Compound

δ, ppm

Multiplicity

Assignment

# of H

cis-MoO 2 (S 2 CNEt 2 ) 2

 
  • 1.25 Triplet

-CH 3

12

 
  • 3.80 Quartet

-CH 2 -

8

P

-

-

-

-

   
  • 1.38 Triplet

-CH 3

12

R

 
  • 3.87 Multiplet

-CH 2 -*

8

 
  • 3.93 Multiplet

-CH 2 -*

Y

 
  • 1.42 Triplet

-CH 3

12

 
  • 3.90 Multiplet

-CH 2 -*

8

*diasteriomers

The data shown in Table 4.6 for cis-MoO 2 (S 2 CNEt 2 ) 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 1 H-NMR spectrum of the same complex showed the presence of a triplet and a quartet at around δ 1.25 and δ 3.80, each corresponding to 4 -CH 3

and 4 -CH 2 - groups, capping the total hydrogen count to 20. Hence, the following structures for cis- and trans- MoO 2 (S 2 CNEt 2 ) 2 were constructed.

and 4 -CH - groups, capping the total hydrogen count to 20. Hence, the following structures

(a)

and 4 -CH - groups, capping the total hydrogen count to 20. Hence, the following structures

(b)

Figure 4.4. (a) cis- and (b) trans- MoO 2 (S 2 CNEt 2 ) 2 .

The formation of the cis- isomer of MoO 2 (S 2 CNEt 2 ) 2 was favored over the trans product because the interaction of the O py -Mo dxy orbitals (p y orbital in oxygen-d xy orbital in molybdenum) of the former preserves the integrity of the π-bonds rendering its stability over the latter. Aside from this, the cis-isomer can also form two σ bonds using the Mo d z 2 and O 1pz orbitals, and the Mo d x 2 - y 2 and O 2px atomic orbitals. On the contrary, the extent of interaction between the O py - Mo dyz orbitals (p y orbital in oxygen and d yz 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 σ bond, involving the Mo d z 2 and O 1pz orbitals.

and 4 -CH - groups, capping the total hydrogen count to 20. Hence, the following structures

Figure 4.5. The p bonding interactions of the filled p orbitals of O 2- 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 1 H-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). 1 H-NMR spectra of compound R revealed

the presence of 20 hydrogen atoms : the presence of a triplet at δ 1.38 corresponding to 4 -CH 3 groups and two multiplets at δ 3.87 and 3.93, signifying two diastereomers of the 4 -CH 2 - 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 -CH 3 groups due to the presence of a triplet at around δ 1.42 and 4 -CH 2 - groups due to a multiplet at around δ 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).

the presence of 20 hydrogen atoms the presence of a triplet at δ 1.38 corresponding to

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

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

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

(4.16)

where n x 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

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

(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

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

(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

Atoms

Mass, g

Atoms

Mass, g

# of Atoms

C

28.75

 
  • 20 10

29.34

 

24.95

10

H

4.85

 
  • 40 20

  • 5.00 4.26

 

20

N

6.65

 
  • 4 2

  • 6.90 5.75

 

2

S

30.85

 
  • 8 4

31.25

 

26.54

4

Cl

-

-

-

 

-

14.86

2

Mo

23.0625

 
  • 2 1

23.40

 

19.9875

1

O

5.835

 
  • 3 1

4.11

 

3.6525

1

Molecular

     

Formula

Mo 2 O 3 (S 2 CNEt 2 ) 4

MoO(S 2 CNEt 2 ) 2

MoOCl 2 (S 2 CNEt 2 ) 2

Adding into the previous data on IR and 1 H-NMR spectroscopy of the compound P, as evident in Table 4.8, the molecular formula deduced was Mo 2 O 3 (S 2 CNEt 2 ) 4 or μ-oxo-tetrakis(N,N- diethyldithiocarbamato)dioxomolybdenum(V), which has the following structure.

Adding into the previous data on IR and H-NMR spectroscopy of the compound P, as evident

Figure 4.7. Elucidated structure of compound P, Mo 2 O 3 (S 2 CNEt 2 ) 4 .

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

Adding into the previous data on IR and H-NMR spectroscopy of the compound P, as evident

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

For compound Y, the molecular formula deduced was MoOCl 2 (S 2 CNEt 2 ) 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.

Adding into the previous data on IR and H-NMR spectroscopy of the compound P, as evident

(I)

(II) (III) Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl (S CNEt )

(II)

(II) (III) Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl (S CNEt )

(III)

Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl 2 (S 2 CNEt 2 ) 2 .

Among the three isomers of MoOCl 2 (S 2 CNEt 2 ) 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-MoO 2 (S 2 CNEt 2 ) 2 provides an environment for the reaction to proceed, and through filtration the undissolved impurities were removed. The purpose of methanol was to dissolve PPh 3 so the latter can react with cis-MoO 2 (S 2 CNEt 2 ) 2 . Treatment of the filtrate with the PPh 3 solution resulted to a nucleophilic type of oxo transfer reaction wherein the oxidation state of Mo changed from VI to IV.

(II) (III) Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl (S CNEt )

(4.16)

As seen in the reaction above, the molybdenum in the complex was reduced while phosphorus in PPh 3 was oxidized. Hence, PPh 3 acted as the reducing agent and as an oxygen acceptor in the reaction. Moreover, swirling and standing caused the following reaction to proceed:

(II) (III) Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl (S CNEt )
(II) (III) Figure 4.9. Elucidated structures of the isomers of compound Y, MoOCl (S CNEt )

(4.17)

Reaction 4.17 shows the condensation of the two reactants to produce the dark purple solid, Mo 2 O 3 (S 2 CNEt 2 ) 4 , which is a binuclear μ-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 PPh 3 was the same as that in the preparation of compound P. PPh 3 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

reacting medium for cis-MoO 2 (S 2 CNEt 2 ) and PPh 3 , 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. PPh 3 was added in excess with respect to cis- MoO 2 (S 2 CNEt 2 ) 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:

reacting medium for cis -MoO (S CNEt ) and PPh , implying that it is unreactive

(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-MoO 2 (S 2 CNEt 2 ). 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.

reacting medium for cis -MoO (S CNEt ) and PPh , implying that it is unreactive

(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 PPH 3 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 PPh 3 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 paper + product, g

+

filter

 

44.6895

  • 33.6330 44.5125

 

Mass of watchglass + filter paper, g

   
  • 33.5003 44.4998

44.4113

 

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

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-MoO 2 (S 2 CNEt 2 ) 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-MoO 2 (S 2 CNEt 2 ) 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 – MoO 2 (S 2 CNEt 2 ) 2 + CH 2 Cl 2

canary yellow solution

1

compound R + CH 2 Cl 2

pink solution

Resulting Mixture

dark red solution

2

compound R+ CH 2 Cl 2 exposed in air

cherry red solution to dark cherry red solution

 

compound R+ CH 2 Cl 2

clear dark red liquid

3

+ H 2 O 2

yellow solution

+excess PPh 3

light cherry red solution

The first reaction performed, as shown in Table 4.10, involved the dissolution of cis – MoO 2 (S 2 CNEt 2 ) 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.

As evidently seen in Table 4.9, the highest percentage yield of 87.12986857% was obtained for compound

(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 CH 2 Cl 2 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:

As evidently seen in Table 4.9, the highest percentage yield of 87.12986857% was obtained for compound

(4.21)

The resulting color of the solution should be yellow-brown, due to the formation of cis – MoO 2 (S 2 CNEt 2 ) 2 , instead of dark cherry red. The oxo transfer reaction that occurred is nucleophilic, wherein O 2 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 CH 2 Cl 2 and addition of excess PPh 3 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.

The resulting color of the solution should be yellow-brown, due to the formation of cis –
The resulting color of the solution should be yellow-brown, due to the formation of cis –

(4.22)

(4.23)

Reaction 4.22 is a nucleophilic reaction, wherein H 2 O 2 acts as an oxidizing agent and as an oxo- donor, causing the oxidation of Mo IV to Mo VI . The reaction yielded the yellow-brown cis – MoO 2 (S 2 CNEt 2 ) 2 as intermediate. Succeedingly, reaction 4.23 also proceeds in a nucleophilic oxo transfer fashion, wherein PPh 3 served as the reducing agent and oxo-acceptor, causing the reduction of Mo VI to Mo IV . The initial red molybdenum complex, compound R (MoO(S 2 CNEt 2 ) 2 ), was again produced in the reaction.

The 20 th 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).

Figure 4.10. A general schematic representation of the extended structure of the molybdenum sites in enzymes

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 4.10. A general schematic representation of the extended structure of the molybdenum sites in enzymes

Figure 4.11. Tabular illustration of stoichiometric formulations for substrate reactions of molybdenum enzymes.

20 | E x e r c i s e

4

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.

Nitrate reductases play key roles in the first step of biological nitrogen cycles i.e., assimilatory ammonification

(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.

Nitrate reductases play key roles in the first step of biological nitrogen cycles i.e., assimilatory ammonification

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).

II. Summary and Conclusion

The experiment first employed the preparation of the oxomolybdenum complex, cis- MoO 2 (S 2 CNEt 2 ) 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-MoO 2 (S 2 CNEt 2 ) 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 σ and π 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-MoO 2 (S 2 CNEt 2 ) 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 PPh 3 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, 1 H-NMR and mass spectroscopy data, compound P was found to be a binuclear μ-oxo species with a molecular formula of Mo 2 O 3 (S 2 CNEt 2 ) 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- MoO 2 (S 2 CNEt 2 ) 2 and PPh 3 , 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, 1 H-NMR and mass spectroscopy, it was revealed that compound R has a molecular formula of MoO(S 2 CNEt 2 ) 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-MoO 2 (S 2 CNEt 2 ) 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, 1 H-NMR and mass spectroscopy data, the molecular formula of compound Y was found to be MoOCl 2 (S 2 CNEt 2 ) 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-MoO 2 (S 2 CNEt 2 ) 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 – MoO 2 (S 2 CNEt 2 ) 2 and compound R in CH 2 Cl 2 gave a dark red solution, which should have been dark violet due to the formation of the purple

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 O 2 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 H 2 O 2 in a CH 2 Cl 2 solution of compound R resulted to a yellow solution indicating the formation of cis-MoO 2 (S 2 CNEt 2 ) 2 . Furthermore, excess PPh 3 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 H 2 O 2 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, 2 nd 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.

Calculations

  • 1. Molecular Formula

    • a. Purple Compound, P

      • i. Number of moles of C, N, H and S

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

ii.

Number of C, N, H and S atoms

Calculations 1. Molecular Formula a. Purple Compound, P i. Number of moles of C, N, H
Calculations 1. Molecular Formula a. Purple Compound, P i. Number of moles of C, N, H
iii. Mass of Mo and O iv. Number of atoms of Mo and O
iii.
Mass of Mo and O
iv.
Number of atoms of Mo and O
iii. Mass of Mo and O iv. Number of atoms of Mo and O v. Molecular
iii. Mass of Mo and O iv. Number of atoms of Mo and O v. Molecular
  • v. Molecular Formula Mo 2 O 3 C 20 H 40 N 4 S 8 or Mo 2 O 3 (S 2 CN(CH 2 CH 3 ) 2 ) 4 or Mo 2 O 3 (S 2 CNEt 2 ) 4

  • b. Red Compound, R

    • i. Number of moles of C, N, H and S

b. Red Compound, R i. Number of moles of C, N, H and S ii. Number
b. Red Compound, R i. Number of moles of C, N, H and S ii. Number

ii.

Number of atoms of C, N, H and S

b. Red Compound, R i. Number of moles of C, N, H and S ii. Number

iii.

Mass of Mo and O

1

mole Mo

2

 

4

S

2

x

C

x

N

x

C

2

x

x

2

 

moles S

 

moles Mo 1

 

2

mass Mo

 

mass O

 

100

g

mass O

100

g

From the data S C

mole S

 

2

CN C

2

H

5

2

10

H

20

N

2

or S

4

C

2

N

2

C

4

H

10

2

H

5

x

2

S

2

2

C

2

N

2

C

2

2

H

5 2

2

CN C

2

H

5

2

410 g P

100 g

95.94 g Mo

P

1 moles Mo

 

m

C

 

m

H

 

m

N

m

S

m

Mo

29.34

g

5.00

g

6.90

g

 

31.25

g

23.4

1 moles Mo 1 moles P

  23.4 g

g

4.11

1 moles P

g

iv.

Number of atoms of Mo and O

iii. Mass of Mo and O 1 mole Mo  2 4 S 2  x
  • v. Molecular Formula MoOC 10 H 20 N 2 S 4 or MoO(S 2 CN(CH 2 CH 3 ) 2 ) 2 or MoO(S 2 CNEt 2 ) 2

  • c. Yellow Compound, Y

    • i. Number of moles of C, N, H and S

c. Yellow Compound, Y i. Number of moles of C, N, H and S ii. Number

ii.

Number of atoms of C, N, H and S

g  mol C  2.07743547 moles    480 9.971690256  10  
g
mol
C
 2.07743547
moles    480
9.971690256
10
  
100
g
g
mol
H
 4.226190476
moles    480
20.28571428
20
  
100
g
g
mol
N
 0.4104211278
moles    480
1.970021413
2
100
g
   
g
mol
S
 0.8275647022
moles    480
3.972310571
4
100
g
   
g
mol
Cl
 0.4191819464
moles    480
2.012073343
2
  
100
g

iii.

Mass of Mo and O

1

mole Mo

2

mole S

2

CN C

2

H

5

2

From the data S C

4

10

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

2

2

C

2

N

2

C

2

2

H

5 2

x

2

 

moles S

2

CN C

2

H

5

2

2

moles Mo 1

mass Mo

1 moles Mo 1 moles P

95.94 g Mo

100 g P

  19.9875 g

 

mass O

100

1 moles P

g

m

C

m

480 g P

H

m

N

m

S

1 moles Mo

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

iii. Mass of Mo and O 1 mole Mo  2 mole S 2  CN
iii. Mass of Mo and O 1 mole Mo  2 mole S 2  CN
  • v. Molecular Formula MoOC 10 H 20 N 2 S 4 Cl 2 or MoOCl 2 (S 2 CN(CH 2 CH 3 ) 2 ) 2 or MoOCl 2 (S 2 CNEt 2 ) 2

  • 2. Percentage Yield a. cis-MoO 2 (S 2 CNEt 2 ) 2

% Yield

Experimental Yield

Theoretical Yield 0.5362 g

100%

1.01386 g

100%

%

Yield

52.88698637%

  • b. Compound P

% Yield

Experimental Yield

100%

Theoretical Yield 0.1327 g 100%

0.3324089307 g

%

Yield

39.92070842%

  • c. Compound R

% Yield

Experimental Yield

100%

Theoretical Yield

0.2782

g

0.3192934921 g

100%

%

Yield

87.12986857%

  • d. Compound Y

% Yield

Experimental Yield

100%

Theoretical Yield

0.0127

g

0.1919895496 g

100%

%

Yield

6.614943378%