Synthesis Of Metal Acetyacetonates Biology Essay

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FTIR (Fourier Transform Infrared) is the measurement technique to the infrared absorbed by molecule which is shown by spectra. Almost all molecules absorb infrared. However, some molecules like He, Ar, Ne which are monoatomic and O2, H2 and so on which are homopolar diatomic molecules do not absorb IR. This is because they do not have dipolar moment. Dipolar moment affected whenever molecules absorb the IR at those frequencies. Dipolar moment is the different in charges in the electronic field in a molecule. Molecules that have dipolar moment will allow infrared photons to interact with the molecule and causes the molecules become excite to higher vibrational states. Since monoatomic and homopolar diatomic molecules do not have dipolar moment, hence, they cannot absorb IR.

As we know, the classical model of an atom is the electrons move in orbits around the nucleus. This gives us the ideas about the responds of atom to an electrical field. Therefore, a magnetic moment associated with each orbiting electron. According to Faraday's law, each circuit will induce an electromotive force and the current will change. However, there is no resistance to motion of electrons in an atom, and therefore the induced current will persist indefinitely. And only when the applied field is removed, the opposite and equal induced current will cancel out the initial induced current.

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The induced current has given rise to an extra magnetic moment in each orbital. Hence, according to the Lenz's law, the resulting magnetic moment is in opposite direction to the field that are having induced current. Hence, when a substance places in a magnetic field, there will be field induced motion of electrons of the material which generate magnetic moment that opposite to the applied field. As the result, the stronger part of a non-uniform magnetic field will repel the material. This phenomenon is called as diamagnetic. However, diamagnetic effect only exists whenever all substances all placed in the magnetic field and diamagnetic effect only for those materials which have all paired spins.

Electrons in a pair spin in opposite directions. So, when electrons are paired together, their opposite spins cause their magnetic fields to cancel each other. Therefore, no net magnetic field exists. It is diamagnetism.

Materials have all paired spins called diamagnetism, how about those materials which have unpaired spins? The materials that have unpaired spin are called as paramagnetic. Paramagnetic substances are substances that contain one or more unpaired electrons. When a paramagnetic substance places in the external magnetic field, the permanent atomic or molecular magnetic moments align themselves in the same direction as the field.

Electrons in a pair spin in same directions. So, electrons are unpaired, it is attracted into a magnetic field. Therefore, it is paramagnetism.

nucleus

electron

Sherwood magnetic susceptibility balance MSB Mk1 can be used to calculate the mass susceptibility. MSB Mk1 is an instrument to measure the magnetic, it can determine whether the complex is paramagnetic or diamagnetic. Then, the instrument will show the reading to indicate the magnetic of the complex. The empty sample tube of the instrument,R0 is always negative value, so it is diamagnetic. Hence, when the reading of complex,R shown is negative value, this can prove that the complex is diamagnetic complex; whereas if the R shown is positive value, then the complex is paramagnetic complex. Then, mass susceptibily, χg is calculated using:

Cbal ⨯ l ⨯ (R - R0)

109 ⨯ m

χg = , where

Cbal = the balance calibration constant

l = the sample length (cm)

m = mass of the sample (g)

R = the reading for tube plus sample

R0 = the reading for empty tube

And then, the mass susceptibility can be further changed to molar susceptibilty. Molar susceptibility is used for easy comparison, since all of the complexes do not have same mass. Then molar susceptibility can be calculated by using the mass susceptibility,χg times molar weight.

Classification of material according to magnetic properties.

Class

Magnitude of susceptibility, χ

Temperature of variation of χ

Structure on atomic scale

Examples

Diamagnetic

Approximately -10-6 to -10-5

Constant

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Atoms have no permanent dipole moment

Noble gases, many metals such as Cu, Hg; non- metal such as Si, P; ions such as Na+; most organic compounds

Paramagnetic

Approximately 10-5 to 10-3

Χ = C/T

Atoms have permanent dipole moment. Neighbouring moment do not interact

Some metals such as Cr, Mn; some diatomic gases such as O2, NO; ion of transition metals, rare earth metals and their salt.

Method:

To prepare tris(acetylacetonato)manganese(III), Mn(acac)3

5g (0.025 mol) manganese (II) chloride tetrahydrate (M. W. 197.90) and 1.3g(0.0095mol) sodium acetate trihydrate (MW 136.08) were dissolved in 200 cm³ distilled water.

21 cm³ of acetyacetone was added to the solution slowly.

The two phase system was treated with 1g/(50 cm³ of water) of potassium permanganate solution.

After a few minutes, 13g/ (50 cm³ of water) of sodium acetate solution was added into the solution.

The solution was heated with stirring at 60oC for 30 minutes.

The resultant solution was cooled in ice-cold water and then the solid complex formed was filtered by suction filtration.

The complex was washed with acetone and it was dried by suction.

To prepare chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2.

6g ammonium chloride was dissolved in 40 cm³ conc. ammonia in a 250 cm³ flask.

The solution was stirred continually. At the same time, 12g of finely powdered CoCl2.6H2O was added in small portions

The slurry in fume cupboard was warmed and 10 cm³ of 30% hydrogen peroxide was added slowly from a burette with vigorous swirling.

When effervescence had ceased, 40 cm³ of concentration hydrochloride acid was added slowly.

The product was heated on a stream bath for 15 minutes.

The product was cooled, filtered and washed with 25 cm³ of ice water, then with 25 cm³ of 6M HCl and then alcohol.

The product was dried at 110oC for an hour.

To prepare aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)].

2 g of vanadium (V) oxide was weighed out into a 250 cm³ conical flask.

A mixture of 5 cm³ of distilled water, 4 cm³ of concentrated sulphuric acid and 10cm³ absolute ethanol were added into the vanadium oxide.

The mixture was heated under reflux for around 1 hour.

The solution was filtered and the filtrate was transfer into a 250 cm³ beaker.

5 cm³ of acetylacetone was added into the solution and then the solution was neutralize by adding 16% w/v of sodium carbonate.

The precipitate was washed with cold methylated spirits and cold ethanol using suction filtration.

The product was dried by suction and the yield was measured.

Half of the product was used for recrystallization.

The half product that for recrystallization was dissolved in a minimum volume of dichloromethane.

The impurities were filtered and diethyl ether was added until precipitation had occurred.

The product was filtered and it was washed with ether and also air dried.

Result:

Mass of product yield

Complex

Mn(acac)3

[CoCl(NH3)5]Cl2

[VO(acac)2(H2O)]

Mass of sample tube + product (g)

16.987

20.886

18.450

Mass of sample tube (g)

13.305

13.148

13.100

Mass of product (g)

3.682

7.738

5.350

Mass Susceptibility

Complex

Mn(acac)3

[CoCl(NH3)5]Cl2

[VO(acac)2(H2O)] (impure)

[VO(acac)2(H2O)] (pure)

Mass of sample tube + product (g)

0.8168

0.8163

0.8168

0.8195

Mass of sample tube (g)

0.8698

0.8867

0.8771

0.8863

Mass of product (g)

0.053

0.0704

0.0603

0.0668

R0

-36

-32

-20

-38

R

866

-35

103

147

Length (cm)

1.7

2.0

2.0

1.5

Mass susceptibility, χg (erg • G-2 •g-1)

2.8932 x 10-5

8.5227 x 10-8

4.0796 x 10-6

4.1542 x 10-6

Molar susceptibility, χmol(erg • G-2 •mol-1)

0.01028

2.13447 ⨯10-5

1.15416 ⨯10-3

1.17630 ⨯10-3

Calculation:

Percentage yield

tris(acetylacetonato)manganese(III), Mn(acac)3

4Mn2+ + MnO4- + 15CH3COCH2COCH3 5Mn(CH3COCHCOCH3)3 + 4H2O + 7H+

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From the equation,

4mol of Mn2+ will produce 5mol of Mn(CH3COCHCOCH3)3

0.0250mol of Mn2+ will produce 0.0313mol of Mn(CH3COCHCOCH3)3

Mass of Mn(acac)3 = Molar mass ⨯ mol

= 355.286g/mol ⨯ 0.0313mol

= 11.103g

Percentage yield of Mn(acac)3 = ⨯ 100%

= ⨯ 100%

= 33.162%

Chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2

2CoCl2∙6H2O + 8NH3 + 2NH4Cl + H2O2 2[Co(NH3)5Cl]Cl2 + 14H2O

From the equation,

2mol of CoCl2∙6H2O will produce 2mol of [Co(NH3)5Cl]Cl2

0.0580mol of CoCl2∙6H2O will produce 0.0580mol of [Co(NH3)5Cl]Cl2

Mass of [Co(NH3)5Cl]Cl2 = Molar mass ⨯ mol

= 250.445g/mol ⨯ 0.0580mol

= 14.526g

Percentage yield of [Co(NH3)5Cl]Cl2 = ⨯ 100%

= ⨯ 100%

= 53.270%

Aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)]

V5+ + e- V4+

From the equation,

2mol of V2O5 will produce 1mol of [VO(acac)2(H2O)]

0.011mol of V2O5 will produce 0.0055mol of [VO(acac)2(H2O)]

Mass of [VO(ACAC)2(H2O)] = Molar mass ⨯ mol

= 283.16g/mol ⨯ 0.0055mol

= 1.557g

Percentage yield of [VO(acac)2(H2O)] = ⨯ 100%

= ⨯ 100%

= 343.6%

Mass susceptibility

Cbal ⨯ l ⨯ (R - R0)

109 ⨯ m

χg =

tris(acetylacetonato)manganese (III), Mn(acac)3

= 2.8932 ⨯ 10-5 erg • G-2 • g-1

Chloropentaamminecobalt (III) chloride, [CoCl(NH3)5]Cl2

= - 8.5227 ⨯ 10-8 erg • G-2 • g-1

Aquabis(acetylacetonato)oxovanadium (IV), [VO(acac)2(H2O)]

erg • G-2 • g-1

Molar susceptibility

tris(acetylacetonato)manganese (III), Mn(acac)3

erg • G-2 • g-1

erg • G-2 • mol-1

Chloropentaamminecobalt (III) chloride, [CoCl(NH3)5]Cl2

erg • G-2 • g-1

erg • G-2 • mol-1

Aquabis(acetylacetonato)oxovanadium (IV), [VO(acac)2(H2O)]

erg • G-2 • g-1

erg • G-2 • mol-1

Discussion (part 1):

From the result shown, the percentage yield of tris(acetylacetonato)manganese(III), Mn(acac)3 is quite low, this may due to the manganese(II) chloride tetrahydra not yet completely reach in the acetylacetone solution. This will cause the manganese to be washed out during the filtration. Besides, for the chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2, the percentage yield also quite low. This is maybe due to the [CoCl(NH3)5]Cl2 may still in the liquid form and has been washed out when filter. Whereas, for the percentage yield of aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)] is very higher. It is higher than 100% because of present of impurity. It is obvious that the pure compounds have impurity. Hence, I think it maybe is the calculation error.

Molar susceptibility is the induce magnet moment per mole per unit applied field. High molar susceptibility means that the complex is having more unpaired spins. This is because high molar susceptibility will lead to paramagnetic and paramagnetic means the unpaired spin appears in a complex. From the calculation, the molar susceptibility of Mn(acac)3 is higher than molar susceptibility of [VO(acac)2(H2O)]. This is because Mn(acac)3 has more unpaired spins than [VO(acac)2(H2O)]. Hence, it has higher susceptibility than [VO(acac)2(H2O)]. Whereas for molar susceptibility of [CoCl(NH3)5]Cl2 is negative value. This is because molar susceptibility is measure the paramagnetic. Since [CoCl(NH3)5]Cl2 is diamagnetic complex, thus it has negative value.

To Prove the Magnetic Properties of a complex

From the result, the tris(acetylacetonato)manganese(III), Mn(acac)3 and aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)] are diamagnetic whereas chloropentaamminecobalt (III) chloride, [CoCl(NH3)5]Cl2 is a diamagnetic. This is because diamagnetic will show R - R0 or molar susceptibility in negative value whereas paramagnetic will show R - R0 or molar susceptibility in positive value.

The Mn(acac)3 can be existing in both paramagnetic and diamagnetic. This can be proven by the theory of valance bond, as shown as the diagram:

The valance bond diagram for tris(acetylacetonato)manganese(III), Mn(acac)3

Mn3+ ion

3d4 4s 4p

In Mn(acac)3, a low spin complex, it would be represented as

Electron donated from (acac)3

3d 4s 4p

In Mn(acac)3, a high spin complex, it would be represented as

Electron donated from (acac)3

3d 4s 4p 4d

Since the magnetic measured result shown the Mn(acac)3 is paramagnetic, thus we can conclude that In Mn(acac)3 is in high spin complex. This is because high spin complex is the only one complex that produces unpaired electrons.

Besides, we can further use ligand field theory to prove the accuracy of the data. In this theory, this octahedral complex is considered does not have π bonding. The diagram below shows that the molecular orbital energy level diagrams of tris(acetylacetonato)manganese(III), Mn(acac)3. Before that, the diagram is drawn based on the VB theory that is Mn(acac)3 is in high spin form.

As the diagram shown, the result obtained is proven as correct result, because this complex can exist in high spin formed.

The chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2 can be existing in both paramagnetic and diamagnetic. This can be proven by the theory of valance bond, as shown as the diagram:

The valance bond diagram for chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2

Co3+ ion

3d5 4s 4p

In [CoCl(NH3)5]Cl2, a low spin complex, it would be represented as

Electron donated from Cl(NH3)5

3d 4s 4p

In [CoCl(NH3)5]Cl2, a high spin complex, it would be represented as

Electron donated from Cl(NH3)5

3d 4s 4p 4d

Since the magnetic measured result shown the [CoCl(NH3)5]Cl2 is diamagnetic, thus we can conclude that [CoCl(NH3)5]Cl2 is in low spin complex. This is because low spin complex is the only one complex that produces all paired electrons.

Besides, we can further use ligand field theory to prove the accuracy of the data. In this theory, this octahedral complex is considered does not have π bonding. The diagram below shows that the molecular orbital energy level diagrams of chloropentaamminecobalt(III) chloride, [CoCl(NH3)5]Cl2. Before that, the diagram is drawn based on the VB theory that is [CoCl(NH3)5]Cl2 is in low spin form.

As the diagram shown, the result obtained is proven as correct result, because this complex can exist in low spin formed.

At last, the aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)] can only be existing in paramagnetic. This also can be proven by the theory of valance bond, as shown as the diagram:

Aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)]

3d 4s 4p

V4+ ion

In Mn(acac)3, a low spin complex, it would be represented as

Electron donated from (acac)2 and H2O

3d 4s 4p

Since the magnetic measured result shown the [VO(acac)2(H2O)] is paramagnetic, thus we can conclude that [VO(acac)2(H2O)] is in low spin complex and this just proven by the valence bond theory. This is because aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)] only can exist in unpaired spin form.

Besides, we can further use ligand field theory to prove the accuracy of the data. In this theory, this octahedral complex is considered does not have π bonding. The diagram below shows that the molecular orbital energy level diagrams of aquabis(acetylacetonato)oxovanadium(IV), [VO(acac)2(H2O)]. Before that, the diagram is drawn based on the VB theory that is [VO(acac)2(H2O)] is in low spin form.

As the diagram shown, the result obtained is proven as correct result, because this complex can exist in low spin formed.

FTIR Spectrum

In FTIR spectrum is summarised as the table below:

Complex

Absorption band (cm-1)

Description

Mn(acac)3

2996.6 &2919.7

Indicate the present of sp3 stretching C-H bond

1591.6 &1506.0

Indicate the present of stretching C=C bond

1386.9

Indicate the present of stretching C-O bond

1255.0

Indicate the present of stretching C=O bond

1015.8

Indicate the present of Mn=O bond

774.6

Indicate the present of Mn-O bond

[CoCl(NH3)5]Cl2

3258.0

Indicate the present of streching N-H bond

487.6

Indicate the present of Co-N bond

[VO(acac)2 (H2O)](impure)

~ 2950

Indicate the present of sp3 stretching C-H bond

1571.6 &1505.5

Indicate the present of stretching C=C bond

1410.6

Indicate the present of stretching C-O bond

1287.4

Indicate the present of stretching C=O bond

936.0

Indicate the present of V=O bond

[VO(acac)2 (H2O)](pure)

~ 2950

Indicate the present of sp3 stretching C-H bond

1534.1

Indicate the present of stretching C=C bond

1418.9

Indicate the present of stretching C-O bond

1286.4

Indicate the present of stretching C=O bond

935.6

Indicate the present of V=O bond

The impure [VO(acac) 2 (H2O)] has a lot of peaks at the region 1500cm-1 to 1600cm-1 whereas pure [VO(acac) 2 (H2O)] does not have so many peaks as the impure. This may due to the impurity of present in the [VO(acac) 2 (H2O)].

Discussion (part 2):

© Copyright all diagrams are drawn by KY Loo, 2010 by using Symyx Draw

1. tris(acetylacetonato)manganese (III), Mn(acac)3

The resonance forms of acetylacetonate are

Resonance of acetylacetonate

Structure of tris(acetylacetonato) manganese(III), Mn(acac)3

2. Chloropentaamminecobalt (III) chloride, [CoCl(NH3)5]Cl2

Structure of Chloropentaamminecobalt (III) chloride, [CoCl(NH3)5]Cl2

aquabis(acetylacetonato)oxovanadium (IV), [VO(acac)2(H2O)]

Structure of aquabis(acetylacetonato)oxovanadium (IV), [VO(ACAC)2(H2O)].

Insulin-mimetic

Diabetes is a disease of carbohydrate metabolism or result of altered lipid or fat metabolism. Diabetic patients can be treated by insulin therapy. However, the insulin therapy will increase the risk of hypoglycaemia or low blood glucose. Hence, vanadium coadministration with insulin is suggested to help to maintain and control the blood glucose level. In another word, the vanadium administration will alleviates many diabetes altered changes in enzyme activity even gene expression but without affect these process in normal organisms.

After some researches, the vanadium complex which is (4-hydroxypyridine-2,6-dicarbosylato)oxovanadate(V) is found out that it has antidiabetic properties. This is because vanadium that present in the muscle will inhibit the plasma membrane ion pumps. Hence, the vanadium has shown to have insulin like effect on glucose metabolism. This shows that vanadium has similar effect with the insulin. However, there are some different effects with insulin. Thus, antidiabetic influence of the vanadium can be considered insulin enhancing but not insulin mimetic. This is because insulin cannot be totally substituted by vanadium compound for the diabetes in any type of the diabetes that requires insulin. Hence, the terms insulin-mimitic or insulin-like that appear in the literature for action of vanadium cannot be classified as similar to or different from the insulin.

Diagram shows the interactions of vanadium with insulin signal transduction cascades.

Anticancer and Nucleolytic

In year 1979, science had found out that biscyclopentadienyldichloro-Vanadium(IV), (C­5H5)VCl2 had antitumor activity. This is because this complex inhibits the growth of various cancer cell lines and the growth of solid tumors in vivo. Nowadays, the vanadocene compounds have found out that can induce the apoptosis in cell lines. The apoptosis of vanadoncene complexes mostly use in metal cancer therapeutic agent. This mainly due to it will trigger the primary DNA damage and involves p53 induction. P53 protein is a tumor suppressor that has 53 kilodaltons molecular mass which function in the process of apoptosis, cell cycle control (mitosis and meiosis) and maintenance of genomic stability.

From the research, the vanadium compounds have inhibited the induced hepatocarcinogenesis by limiting cell proliferation and chromosomal aberrations in this cancer preneoplastic stages of development. Vanadate has proven that it is effective to against the induction of colon carcinomas and vanadium(III) cysteine compound also has been proven that has antimetastatic effects against lung metastases. Nowadays, the metvan, bis(4,7 -dimethyl-1,10-phenanthroline)sulfatooxovanadium(IV) is the new broad spectrum anticancer vanadium drug. It has favourable pharmacodynamics features and very low toxicity to the human. Thus, in primary human leukemia cells, it is more effective to induce apoptosis than standard chemotherapeutic agents.

Besides, vanadium complex also induce antineoplastic cell cycle arrest or cytotoxic effect through DNA cleavage (nucleolytic). Then it undergoes fragmentation and plasma membrane lipoperoxidation reactions, the mediated is assumed via the effect of cellular redox chemistry. In fact, the nucleolytic properties are applied in the anticancer properties. This is because to kill the cancer cell, vanadium complex besides apoptosis, it also can cleave the DNA or RNA of the tumor cell, so that the cell death automatically.

Vanadium interaction with some apoptotic signal transduction pathways.

Both diabetes and cancer are actually same family of disease with different metabolic alterations. Besides, both diseases have involved same phosphorylation cascade and utilize transcription factors that control in variations of low level of reactive oxygen species (ROS) and nitrogen reactive species (NOS). Both ROS and NOS initiate the apoptosis when it is administered as therapeutic agent for diabetes and cancer. Then, the vanadium complex acts as the therapeutic agent for both diseases by alter the signal transduction process. The major signal transduction pathway for diabetes is growth hormone pathways whereas the major signal transduction pathway for cancer is the apoptosis pathway.

Conclusion:

The complexes have prepared and their percentage yields have calculated respectively as show in the calculation part.