Title: Synthesis of Cu(II)-Tetraphenylporphinate Aim: The experiment has a two-part aim: (a) to synthesise meso-tetraphenylporphyrin (H2TPP) by the reaction

between pyrrole (C4H4NH) and benzaldehyde (C6H5CHO) in refluxing propanoic acid (CH3CH2COOH), (b) as well as to observe the reaction between the ligand and Copper acetate monohydrate in refluxing N, Ndimethylformamide. The product is a Copper (II) metalloporphyrin complex (CuTPP). H2TPP is characterised by its 1H NMR spectrum as well as UV spectrum and its molar absorption coefficient. CuTPP is characterised by UV spectrum and its molar absorption coefficient. Percentage purity is included in each step to assess the experimentation. Data and Results (Data sheet is attached as Appendix A) Calculations Part A Table 1: Compound Mass Volume (g) (cm3) C6H5CHO NA 1.7 C4H4NH NA 1.0 CH3CH2COOH NA 40.0

Density (g/ cm3) 1.04 0.967 0.990

R.M.M. (g/ mol) 106.12257 67.08957 74.078540

Amount (mol) 0.016660 0.014414 0.53457

Limiting Reagent NA

Theoretical amount of C44H30N4 (H2TPP) expected = (0.014414/ 4)(614.7358) = 2.2152 g Experimental amount of H2TPP obtained = 0.8014 g Percentage yield = experimental yield/ theoretical yield = 0.8014/ 2.2152 x 100 = 36.177% Observation: Colourless solution turns yellow then orange and finally dark purple-brown upon dropwise addition of C6H5CHO AND C4H4NH down the wall of condenser. Upon filtration, vibrant purple crystals found. The UV Spectrum of H2TPP is attached as Appendix B, 1H NMR Spectrum of H2TPP as Appendix C. Part B Table 2: Compound H2TPP Cu(COOCH3)2H2O N,N-Dimethylformamide (DMF) Mass (g) 0.1061 0.2310 NA Volume (cm3) NA NA 20.0 Density (g/ cm3) NA NA 0.944 R.M.M. Amount (g/ mol) (mol) 614.7396 0.00017259 199.64932 11.570 73.09412 0.25830 Limiting Reagent NA

Theoretical amount of CuC44H28N4 (CuTPP) expected = (0.00017259)(676.265920)= 0.11672 g Experimental amount of CuTPP obtained = 0.0250 g Percentage yield = 0.0250/ 0.11672 = 21.419 % Observation: Solution turns from purplish-blue to red solution upon reflux. At separatory funnel, a light blue-green layer is above a dark red layer. In column, broad red layer is eluted faster than a sharply-defined tarry layer. Red solution eluted is rotary evaporated to obtain reddish purple crystals. The UV Spectrum of CuTPP is attached as Appendix D. Part C For UV spectroscopy analysis of H2TPP: Dilution Factor for series dilution = 100/1 = 100 Concentration of initial solution = (0.0141 g/ 614.7358gmol-1) x (1000/ 100 cm3) = 2.2937 x 10-4 M Concentration of final solution = 2.2937 x 10-4 M/ 100 = 2.2937 x 10-6 M For UV spectroscopy analysis of CuTPP: Dilution Factor for series dilution = 100/1 = 100 Concentration of initial solution = (0.0038 g/ 678.2859 gmol-1) x (1000/ 100 cm3) = 5.6023 x 10-5 M Concentration of final solution = 5.6023 x 10-5 M/ 100 = 5.6023 x 10-7 M Table 3: Calculated molar absorptivity coefficients (in 4 significant figures) from the wavelength and absorbance for each compound. Its accuracy is limited by the number of significant values of the Absorbance. Compound Wavelength Absorbance Molar absorptivity

H2TPP

CuTPP Discussion i. General Discussion

() 419.00 514.50 549.50 589.50 649.00 416.00

(A) 0.7306 0.0302 0.0137 0.0104 0.0117 0.0797

coefficient () 318500 13170 5973 4534 5101 142300

4 C6H5CHO + 4 C4H4NH + 3/2 O2 C44H30N4 + 7 H2O H2TPP + Cu(O2CCH3)2(H2O) Cu(TPP) + 2 HO2CCH3 + H2O Part A

Equation 1 Equation 2

This experiment utilises the Alder-Longo method to synthesise H2TPP (See Equation 1)[1], before proceeding with the metallation of the porphyrin, forming CuTPP. The Alder-Longo method begins with a protonation of carbonyl oxygen to result in a favourable nucleophilic addition by pyrrole (Scheme 1). An acidic medium (Propanoic acid) was used to yield H+ to protonate benzaldehyde or methanol analogue to promote the nucleophilic addition of the compound by pyrrole or its substituted form. Protonation of benzaldehyde is followed by the release of a proton to solution to stabilise positively-charged Nitrogen, and protonation of methanol analogue is followed by the formation of water. Formation of water is favoured as OH is a better leaving group than H. The reaction continues until the mesotetrasubstituted porphyrin ring is completed. Propanoic acid is used instead of acetic acid, which gives 20-25% higher yield, because the resulting product does not crystallize easily due to the high pKa of acetic acid, making isolation and purification more difficult [2]. Boiling chips are added to achieve smooth boiling, and this is necessary to avoid loss of product if the solution refluxes through the condenser. This reaction is carried out in open air as Oxygen is necessary to oxidise porphyrinogen to porphyrin ring by loss of 6 electrons. After reflux, the purple crystals are collected by suction filtration and washed with methanol to remove polar organic impurities and propanoic acid present. The crystals were then left to dry by drawing air through them for a few minutes before measuring the dry mass. Loss of yield in transfer is minimised by transferring the product onto a weighted filter paper before measuring the overall weight. The dry mass of the crystals is the difference between the overall weight and the weight of filter paper alone. This procedure, which is repeated for Part A and C, utilises the least transfer of yield and so minimises yield loss. The extended conjugation throughout the system significantly increased the wavelength of absorption that promotes electrons from to *. The extended conjugation arises from overlapping p-orbital of each Carbon and Nitrogen in the system. The wavelength of absorption that promotes the electron from HOMO to LUMO is in the range of 560 nm to 600 nm, so the complementary color given out is violet. A less significant colour contribution arises from the n to * transition due to the lone pair from Nitrogen, but its occurrence is forbidden and its effect is drowned by the allowed to * transition. The percentage yield is 36.177%, which is much higher than the literature value of 20%. Loss in yield is caused by incomplete reaction and loss in transfer from Hirsch funnel to weighted filter paper. The reaction is not complete as all the reactions are in equilibrium, with the exception of oxidation, which is a driving force in the reaction. Loss of proton to solution is not largely favourable as the solution is acidic and has an excess of protons. The spontaneity on the loss of proton solely arises from the enthalpy of stabilisation when Nitrogen loses its positive charge. However, the yield is not pure as a possible contaminant, meso-tetraphenylchlorin, could be present. This compound is identical to H2TPP except for the locations of double bonds in the complex. Hence the reported yield for H2TPP is likely to be overestimated. This is supported by UV-Vis spectrum obtained for H2TPP, which has an absorbance peak at 649 nm (See Table 3). This peak has a higher absorbance than expected for the last Q-band (0.0117 at 646 nm versus the lower 0.0104 at 589.50 nm), and as such could have contribution from chlorin (650 nm) as well. Although this impurity is later removed through column chromatography (See Part C), significant loss of porphyrin itself occur due to adsorption to the stationary phase, as observed in Part C, and so the yield ought to be maximised in the early stage.

An improvised experimentation would be the use of 2,3-Dichloro-5,6-Dicyanobenzoquinone (DDQ) to oxidise the chlorin to H2TPP. Progress of reaction could be monitored by the leftward shift of the Q-band to 646 nm, and a reduced absorbance for the peak.

Scheme 1: The synthesis of H2TPP via nucleophilic addition to Carbonyl Carbon, concurrent to protonation of Carbonyl Oxygen. Throughout the steps, nucleophilic addition to benzaldehyde is followed by loss of proton, and nucleophilic addition to methanol analogue is followed by loss of water. In this representation, two methanol analogues

react to give porphyrinogen. However, it is possible for the methanol analogue to continue reacting with 2 benzaldehyde molecules to arrive at the same product. Sketch is made on ACD/ChemSketch Version 11.02. Part B In this step, Cu(II) incorporation into H2TTP is done in the presence of catalytic acetate ion in DMF. DMF is used as a solvent because DMF effect slight dissociation of Cu(COOCH3)2H2O. When the monohydrate acetate is added to DMF, the compound dissociates, as given in the dissociation equilibria below [3]: Cu2+ + CuAc2 2CuAc+ 2CuAc+ Cu2Ac4 Equation 3 Equation 4

CuAc+ is reactive whereas the dimer, Cu2Ac4, is not. Monohydrate form of the compound is experimentally observed to give an improved reaction rate. Presence of water contributes to the ease of dissociation to give acetate ion, increasing the reaction rate. In addition, water from the monohydrate crystal contributes to the destruction of the dimeric structure, giving more acetate ions for the reaction [3]. The mechanism of the reaction has not been established in literature [4], but has been suggested to include an association between the free or complexed metal ion and porphyrin, resulting in the loss of the two inner protons. The rate-determining step has also been linked to deformation of the rigid porphyrin plane [5]. Since there is high energy barrier, reflux is used to provide sufficient energy to the reaction. The final product is a sitting-atop complex of the Cu(II) on the distorted porphyrin plane [6]. After reflux, the reaction mixture is quenched in an ice bath to induce crystallization of CuTPP, and water is added to dissolve unreacted copper acetate. Dichloromethane is used to wash the solution in a separatory funnel because it is much less polar than DMF so it contains the nonpolar CuTPP, and its greater density (1.33 g/ cm3 [7]) compared to that of DMF (0.944 g/ cm3 [7]) means that it can be conveniently removed as it is at the bottom layer (dark red). Unreacted Copper compound remains in the polar DMF, contributing to its blue-green colour. The combined solution from bottom layer of repeated washings is then rotary evaporated. Rotary evaporation is used to remove excess solvent as it is convenient and fast, as compared to heating the solution in an oil bath. The advantage of rotary evaporation arises from its vacuum environment that lowers melting points of solvents, vaporising excess solvents easily. Part C In this part, column chromatography was performed to remove impurities. A mixture of hexane and toluene was used in this experiment. The reduction of polarity by mixing hexane with toluene favours the elution of nonpolar CuTPP. The speed of elution depends on the polarity of the mobile phase, and the equal volume mixture achieves a polarity that is in between hexane (polarity index of 0.1 [8]) and toluene (polarity index of 2.4 [8]). This has been experimentally determined to allow a sufficiently quick elution of the desired product while the impurity layer is eluted much later. A higher elution speed also implies that less of the desired product is adsorbed onto the alumina. Before commencing the chromatography, the crude product was dissolved in a small volume of the mobile phase. This is because, during the elution, the sample would be diluted and a red broad band would be observed. This resulted in more volume collected. A greater volume may result in more impurities being eluted. Hence, to achieve a greater purity, the crude sample was dissolved only in minimal mobile phase solvent. The impurity layer appears as a sharply-defined black tarry layer. This is likely to be polar pyrrolic oligomers that did not cyclicise to form the porphyrinogen. Since the stationary phase is polar, this polar impurity is more strongly adsorbed to it. Another impurity present removed through column chromatography is the meso-tetraphenylchlorin, which has been reported to be present in a range of 2% 10% of the product [9]. Although this product has very low polarity, its removal through column chromatography arises from its small amount and the long column, and so it is not observed in the eluted solution. The eluent is collected and rotary evaporated, before being washed with methanol to give the crystals and filtered. The crystals obtained appear reddish-purple. When Copper is incorporated into the porphyrin ring, the delocalisation connecting the four Nitrogen atoms, observed in H2TPP, is removed, resulting in a slightly reduced wavelength of absorption. There is only a slight reduction as other delocalisation remains for CuTPP. In addition, large d to * transition too occurs due to metal-ligand backbonding. As the compound now absorbs a higher frequency between green and yellow wavelength (about 540 nm to 580 nm), the complementary colour observed is in between violet and red, according to the colour wheel model.

The percentage yield is low at 21.419%. Loss in yield is due to: firstly, the high energy barrier of reaction as large Cu2+ ion has to coordinate to planar H2TPP; secondly, some CuTPP remains in the column due to adsorption, and lastly, the tail end of the red smear (product) was not collected to avoid eluting impurity. The remaining amount of CuTPP in the column, either due to adsorption or close proximity to impurity, is considered as random error. ii. NMR Peak Assignment of the Spectrum and Discussion
b b c c d b c b

H
d

H
d

H
d

b b

d c

N
d

N H
d c b c b b d a

H N
a d c b d c b b

Figure 1: The labelling of all protons on CuTPP. Sketch is made on ACD/ChemSketch Version 11.02. Table 4: The assignment of chemical shifts observed from the given 1H NMR spectrum. Chemical shift Number of Multiplicity Assignment Explanation (ppm) protons Ha have the greatest deshielding effect as they are directly attached to the electronegative N atom. However, as they are in the shielded conical region of porphyrin ring, they become heavily shielded (anisotropy effect). This gives a negative chemical shift value. -2.763 2 Singlet Ha Peak is a singlet because there are no chemically inequivalent, neighbouring protons within 3 bonds. There is the nearest proton is four bonds away. The area integration of 2 further confirms the assignment. Hb are in meta and para position of the phenyl rings, 7.806, 7.802, and experience an anisotropy effect of the benzene 7.788, 7.786, ring, resulting in a chemical shift range of 7 to 8 ppm. 7.779, 7.775, They are chemically equivalent but not magnetically 7.770, 7.766, equivalent. 7.759, 7.755, 12 Multiplet Hb 7.751, 7.740, A multiplet is seen because of coupling between 7.737, 7.729, neighbouring protons and overlapping of triplet 7.259 signals. Area integration of 12 confirms the assignment as there are 8 meta protons and 4 para protons. This peak is assigned to be Hc instead of Hd, as it has a high chemical shift value which agrees with the observation that Hc are more deshielded as a result of 8.244, 8.237, anisotropy effect by porphyrin ring. 8.233, 8.223, 8 Multiplet Hc 8.218, 8.213 A multiplet is seen because Hc couple with neighbouring protons, and an overlap of the splits occurred. An area integration of 8 does not disprove the assignment. This is assigned to be Hd which have the highest 8.852 8 Singlet Hd chemical shift value, due to deshielding from the anisotropy effect of porphyrin ring, as well as from an

inductive effect caused by the nearby electronegative N atoms. A singlet is seen because there are no chemically inequivalent, neighbouring protons within 3 bonds. The nearest proton is 6 bonds away. An area integration of 8 does not disprove the assignment. iii. UV-Vis Spectrum Discussion

To describe the absorption spectra of porphyrin, the Gouterman Four Orbital Model is used. The model describes the absorption bands in porphyrin systems that arise from transitions between 2 HOMOs and 2 LUMOs, with the relative energies of the transitions depending on the (electronic) nature of metal center and the substituents on the ring. For CuTPP (D4h symmetry), the HOMOs are nondegenerate a1u and a2u whereas the LUMOs is a set of 2 degenerate eg. Transitions between these orbitals gave rise to two excited states, both of 1Eu character. Since the electronic configuration of a ground state porphyrin is 1A1g (a1u2a2u2) [10], the lowest singlet excited configurations are 1(a2u1 eg1) and 1(a1u1 eg1). However, their near degenerate nature (arising from the close energy levels) resulted in a resonance that gives a lower energy 1Eu state with small strength of transition or oscillator strength, and a higher energy 1Eu state with large oscillator strength. The former is called Q(0,0) band, and the latter, Soret B(0,0) band. In the Q band, the transition dipoles of the two configurations are destructive, and in Soret band, the transition dipoles of the two configurations are constructive. Q bands are observed solely due to the vibronic coupling to the Soret band, as it is forbidden. When H2TTP is metallated with Cu, the peak at 647 nm disappears, and the number of Q bands observed is reduced. This is because of a change in symmetry. H2TTP has D2h symmetry, whereas CuTTP has D4h symmetry. The increase in symmetry of the complex resulted in the reduced number of absorption bands, from 4 Q bands in H2TPP to 0 in CuTPP. When Soret band wavelength is compared between H2TPP and CuTPP, a hypsochromic shift has occurred from 419 nm to 416 nm. This arises from the loss of delocalisation around 4 Nitrogen atoms in TTP, which reduces the wavelength of absorption, as well as large metal-to-ligand charge transfer (MLCT) from the d orbitals of Cu2+ to the * anti-bonding orbital of the porphyrin ligand. Its large absorptivity value of 142 300 M-1cm-1 is because it is Laporteallowed and spin-allowed. This transition is dominant to LMCT, which occur from a1u and a2u of TTP to empty d orbitals, as well as to d-d transitions, which occur within d-orbitals. The reduction in molar absorptivity coefficient of Soret band from 318 500 M-1cm-1 to 142 300 M-1cm-1 suggests that the metallated porphyrin has a reduced property to absorb light. This is an important property given the large application of CuTPP, such as catalysis, where metallation reduces the photocatalytic activity of H2TPP on chloroform [14]. The large coefficient for H2TPP arises from its extensive conjugation. Precautions Taken Gloves are worn throughout the experiment, as chemicals (toluene in elution and chloroform in preparing KBr disc) used are corrosive. The fumehood cover is also pulled down to prevent inhalation of strong vapour of propanoic acid, and volatile dichloromethane, toluene and hexane. Care is taken to ensure boiling chips are placed in rbf before reflux to prevent spillage of refluxing solvent through condenser. For UV spectroscopy, H2TPP and CuTPP are ensured to be fully dissolved as the presence of un-dissolved particles can cause scattering. In addition, for H2TPP, the process is done quickly due to photocatalytic activity of H2TPP on chloroform. The sides of the cuvettes are wiped to minimize scattering of radiation and possible oil presence from fingerprint. Rinsing of cuvettes with solvent and sample solution before filling it up for actual analysis is also done to minimize sample carry over. Conclusion The percentage yield of H2TPP is 36.177% and CuTPP is 21.412%. UV spectrums of the products suggest a hypsochromic shift in the Soret band through the occurrence of complex. The max for Soret band of H2TPP is 419.00 nm with value of 318 500 M-1 cm-1, and that of CuTPP at 410.50nm is 142 300 M-1 cm-1. Reference 1. Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; Marguerettaz, A. M. J. Org. Chem., 52, 827-836 (1987) 2. G. D. Dorough, J. R. Muller, and F. M. Huennekens, J. Am. Chem. Soc., 73,4315 (1951).

3. 4. 5. 6. 7. 8. 9. 10.

Sugata, S.; Matsushimaj, S. Inorg. Nucl. Chem., 39, 729-731 (1975). Pasternack, R.F.; Vogel, G.C.; Skowronek, C.A.; Harris, R.K.; Miller, J.G. Inorg. Chem., 20, 3763 (1981) Turay, J.; Hambright,P. Inorg. Chem, 19, 562-564 (1980). Pasternack, R.F.; Vogel, G.C.; Skowronek, C.A.; Harris, R.A.; Miller, J.G. Inorg. Chem., 20, 11 (1981) CRC Handbook of Chemistry and Physics, 84th ed.; CRC Press: Boca Raton, FL., 2003. Louisiana State University, Polarity Index. URL: http://macro.lsu.edu/howto/solvents/Polarity%20index.htm (9th May 2012) A. D. Adler, F. R. Longo, F. Kampas, and J. Kim, J. Znorg. Nucl. Chem., 32, 2443 (1970). Milgrom, L.R. The Colours of Life: An Introduction to the Chemistry of Porphyrins and Related Compounds, OUP, Oxford, 1997.