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Eiiiii3i3§xé. 253v. :. ....,x¥.13}..xnu§(:la P1-CO-porCu 2.162 2.0A6 200 31 15.3 P1-CH2-porCu 2.158 2.0A6 205 33 16.2 P1-CH2-porCu(B) 2.169 2.039 210 36 17.6 P2-NH-CH2-porCu 2.166 2.0A8 205 36 17.2 P2-NH-CO-porCu 2.162 2.038 215 37 17.1 P3-CH2-O-porCu 2.159 2.037 205 36 17.5 P3-CH2-O-porCU(B) 2.169 2.0AO 205 36 17.3 P3-CH2-NH-porCu 2.167 2.052 210 35 17.2 P3-CH2-py-porCu 2.166 2.052 210 35 17.2 Cu Res-NH-TPP-NH2b 2.182 2.049 199 42 17 Cu Res-CO-TPP-COOHb 2.157 2.07 220 40 15 TPPCu in TPPH2c 2.187 2.0A5 202 33 15 ain gauss ref 1A 0ref 68 AZ 3300 gauss IOO gauss 1———1 Figure 10. ESR spectrum of P3-CH -0-porV0. 2 A3 3300 gauss I 50 gauss M Figure 11. ESR spectrum of Pl-CO-porCu. AA features are not observed in the room temperature spectrum of this complex. Some of the pertinent data are given in Table 6. It will be noted that the ESR parameters for this complex are very similar to those of TPPCu in TPPH2 and those reported by Rollmann for a similarly prepared polymer-bound copper porphyrin“4 For P1-CH -porCu prepared from TPP(CHZOH)u_x(CHZCl)xH2, the poly- 2 mer-bound copper complex gives a well resolved ESR spectrum (Figure 12) very similar to that of P -C0-porCu. In the case of P1-CH -porCu(B) 1 2 prepared from TPP(CHZOH)uCu, the spectrum is again well resolved in Figure 13 although the ESR parameters are somewhat different (see Table 6). Neither of these samples show nitrogen perpendicular splittings at room temperature or at 770K. The copper complex, P -NH-CO-porCu, has an ESR spectrum that is the 2 least resolved of all of the polymer-bound copper porphyrins except perhaps that of P3-CH2-O-porCu(B) which was prepared from P3-CH2-0-Ph- CHO as the starting material. Despite the poorer resolution of P2-NH- CO-porCu's ESR spectrum, the g!!, gL, CUII’ Gui, and the average value of’ the ‘nitrogen superhyperfine splitting ‘were still observable in Figure 1A. PZ-NH-CHZ-porCu has an ESR spectrum that is relatively well re- solved with all but the nitrogen perpendicular superhyperfine structure being apparent at room temperature (Figure 15). Values of g” = 2.166 and 81.: 2.0A8 were easily determined from the spectrum. Also Cu and Cu and were easily obtained. 1. 3400 gauss 100 gauss 1————-1 Figure 12. ESR spectrum of Pl-CHZ-porCu. 46 340|0 gauss 100 gauss 1————1 Figure 13. ESR spectrum of P -CH2-porCu(B). 1 A7 3300 gauss 100 gauss F——"_4 Figure 1A. ESR spectrum of PZ-NH-CO-porCu. A8 3400 gauss I00 gauss 1————1 -NH "CH -pOICUO Figure 15. ESR spectrum of P2 2 A9 P3-CH2-O-porCu and P3-CH2-0-porCu(B) have surprisingly different copper ESR spectra which must reflect the two methods that were used in their preparations. P3-CH2-0-porCu has a relatively well resolved ESR spectrum in Figure 16, whereas P3-CH20-porCu(B) does not (Figure 17). Despite these differences, the two complexes have similar ESR para- meters (see Table 6). In addition to the usually observed lines, nitrogen perpendicular superhyperfine splittings are observable for P - 3 CHZ-O-porCu at room temperature. These lines are found on the m = -3/2 and -1/2 lines of the (kin features. In the case of P3-CH2-NH-porCu and P3-CH2-py-porCu, the ESR spec- tra are very well resolved and clearly show all of the characteristics expected for a copper porphyrin. At room temperature, spectra of both complexes are found to have nitrogen superhyperfine lines on the CuH features of m = —3/2 and -1/2. These features are easily seen in Figures 18 and 19, respectively. IL The Assisted, Free-Radical Autoxidation of Cyclohexene as a Probe for Reactivity of Polymer-Bound Metalloporphyrins. The free-radical oxidation of alkenes and of cyclohexene, in particular, has been shown to be initiated by metalloporphyrins,33’72" 75 37 metallophthalocyanines, and various other transition metal com- 76’77 The commonly obtained oxidation products for cyclohexene plexes. are cyclohexene oxide, 2-cyclohexenone, and 2-cyclohexenol (with the latter two being the major products). Vanadyl porphyrins, cobalt porphyrins, and iron porphyrins have been shown to be effective initiators in the free-radical autoxidation of alkenes. An ESR study by Fuhrhop indicates that activation of 340090uss 100 gauss I———1 Figure 16. ESR spectrum of PB-CHZ-C-porCu. 51 3400 gauss l 100 gauss 1————1 Figure 17. ESR spectrum of PB-CHZ-O-porCMB). 52 3400 gauss 100 gauss 1—-——1 Figure 18. ESR spectrum of P -CH -NH-porCu. 3 2 53 3400 gauss 100 gauss t—l Figure 19. ESR spectrum of PB-CHZ-py-poflu. 5A cyclohexene by cobalt(III) porphyrins is the most likely candidate for 73.7A the initiation step in the autoxidation of cyclohexene. Fuhrhop has also shown that the incubation period for the autoxidation of cyclohexene by cobalt(II) porphyrins is eliminated when the cobalt(III) 73,7A 33 porphyrin is used in place of the cobalt(II) porphyrin. LeDon, 72 73,7A Paulson, and Fuhrhop have shown that the u-oxo iron(III) porphy- rin dimer is necessary for any oxidation of cyclohexene to occur. The initiation of the free-radical autoxidation of cyclohexene by TTPCo, TPP(COZhexyl)uCo, and TTPFeCl was studied as standards for the polymer-bound metalloporphyrins; P3-CH2-0-porCo, P2 P3-CH2-O-porFeCl, respectively. These reactions were run in cyclohex- ene at 60°C in one atmosphere of dioxygen and the reaction was followed -NH-C0-porCo, and with the aid of a gas buret. The products and their relative distribu- tions were determined with a go. TTPCo was found to initiate the autoxidation of cyclohexene imme- diately at 60°C. The rate of dioxygen uptake was followed for two hours by which time the rate had reached a maximum. The rate of dioxygen 1 at 60°C uptake was found to be 20A0 mL of dioxygen min-1mmole of Co- (Table 7). The reaction products were analyzed after 2 hours and after 2A hours. The product distribution after 2 hours was found to be similar to that reported previously with 2-cyclohexenone comprising 70- 75% of the oxidized products, 2-cyclohexenol was 20-25%, and cyclohex- ene oxide was only 2-3%.72 After 2A hours, the relative amounts of the products had changed considerably. The relative amounts were now 2- cyclohexenone, 20-25%; 2-cyclohexenol, 70-75%; cyclohexene oxide, only a trace (Table 8). 55 Table 7 Rates of Dioxygen Uptake qu the Autoxidation of Cyclohexene at 60 C and 1 ATM Catalyst Ratea TTPCOb 2040 TPP(COZhexyl)uCob 1900 TTPFeClb 940 P3-CH2-0-porCoc 900 P2-NH-CO-porCoc 250 used P3-CH2-0-porCoC 570 used P3-CH2-O-porFeClc 357 ground P3-CH2-0-porCod 2850 ground P2-NH-CO-porCoe 1770 a . . -1 -1 me of dioxygen min mmole M 00.5 mg d100 mg A3.A mg e76.6 mg 56 020 HO >.mw w.>m 3.0 o._m :.o Amy Hocmxosoaozonm :.m m._ “av ococoxosoaomoum coaeaeatemaa educate moms» come» moms» women moms» women 0.? women come» moms» moms» Auv m magma ARV ooflxoocoxmnoaomo ocoxosoaozo :N :N 3m :m :N am :N :N N Anv mane com: Hometoa101mmo1md oesosm so: ooeoa1oo1m21ma cczoem com: 306— ooeoa101mmo1md Hoobmfie ooalasxegmocceae oomhe emsaeemc 57 Similar results were found for the autoxidation of cyclohexene when TPP(CO hexyl)uCo was used to initiate the reaction. The rate of 2 dioxygen uptake was 1900 mL of dioxygen min-1mmole of Co-1. Again the product distributions after 2 hours and 2A hours were determined. The relative amounts of each product were similar to the results for when TTPCo was used as the catalyst. When TTPFeCl was used to initiate the autoxidation of cyclohexene, a very short incubation period of less than 5 minutes was observed. The rate of dioxygen uptake was 9A0 mL of dioxygen min-1mmole of Fe-1. After 2A hours, the reaction products had a distribution of 2-cyclohexe- none, 35-A0%; 2-cyclohexenol, 55-60%; cyclohexene oxide, 3-A%. For P3-CH2-0-porCo, the uptake of dioxygen occurred after a short incubation period of less than 10 minutes. The rate of dioxygen uptake was 900 mL of dioxygen min-1mmole of Co-1 for unused, whole beads and 2850 mL of dioxygen min-1mmole of Co-1 for unused, powdered beads. After 2A hours, the product distribution was 2-cyclohexenone (20-25%), 2-cyclohexenol (70-75%), and cyclohexene oxide (trace). Used, whole beads were less active than the unused beads. The used beads have a dioxygen uptake rate of 570 mL of dioxygen min-1mmol of Co.1 which is nearly half the rate of the unused, whole beads. In the case of P2-NH-C0-porCo, the uptake of dioxygen began after an incubation period of about 10 minutes. A rate of 250 mL of dioxygen min-1mmole of Co.1 was found for dioxygen uptake for the whole beads. Once ground, the copolymer, P2-NH-CO-porCo, caused a dioxygen uptake of 1770 mL of dioxygen min-1mmole of Co-1. After 2A hours, the product distribution for whole and ground beads was again similar to that of P - 3 CHZ-O-porCo after 2A hours. 58 In comparison to TTPFeCl, P3-CH2-0-porFeCl was very sluggish in starting the autoxidation of cyclohexene. At 60°C the polymer-bound iron(III) porphyrin, had..a very long incubation period before any dioxygen uptake was noted. No uptake was noted for at least 3 hours and only 6 mL of dioxygen had been taken up after a total of 6 hours. In comparison, several experiments for other samples (Co) absorbed about 1 mL of dioxygen in only one minute. Used beads had an incubation period of only 20 minutes and an uptake rate of 360 mL of dioxygen min-1mmole of Fe-1. The ratio of products after 2A hours was similar to those of the other reactions after 2A hours. In all of these reactions, the metalloporphyrins were susceptible to decomposition. Fuhrhop has indicated that this decomposition can result. in. colorless solutions.73 In this work, solutions of the metalloporphyrins and the polymer-bound metalloporphyrins bleached con- siderably during the 2A hour period (Figure 20), because the porphyrin ring is susceptible to attack by free radicals that are generated in the autoxidation of cyclohexene. Rollmann also reported that the decompo- sition of TPPCo and the polymer-bound cobalt porphyrins occurs during the free-radical oxidation of butanethiol1u that can be catalyzed by cobalt porphyrins. From used P3-CH2-O-porCo, it is apparent from its rate of dioxygen uptake (Table 7) that a considerable amount of polymer- bound cobalt porphyrin must have decomposed during the first run when its rate is compared to that of the unused beads. 59 “II.-"K- l l l 500 550 600 650nm Figure 20. Decomposition of TPP(COZhexyl)uCo during autoxidation of cyclohexene. 60 I. The Assisted Autoxidation of Aldehydes. The autoxidation of aldehydes may be initiated either thermally or photochemically, or by metallated polyphthalocyanines and metallopor- 79 have investigated both the thermally phyrins. Zaikov and coworkers and. photochemically' initiated autoxidation of several aldehydes in organic solvents. Osa and coworkers have studied the liquid phase autoxidation of aldehydes in the presence of metallated polyphthalocy- . 80,81 81-83 anines and metalloporphyrins. The autoxidation of benzaldehyde and of butanal were subjected to a preliminary investigation. The autoxidations were carried out in the 1-CO-porCo(B), and P1-CO- porFeCl(B). These oxidations of benzaldehyde and butanal to their presence of the following: TPP(COZEt)uCo, P respective peracids were performed in ethyl acetate which Osa showed was a good solvent for the autoxidation of various aldehydes.80 The reaction conditions were 25 mL of a solution consisting of 0.09 mM in TPP(C02- Et)uCo and 0.5 M in aldehyde at 30°C and 1 ATM of 0 A 0.100 g portion 2. of beads was used in place of TPP(C02Et)uCo when the polymer-bound metalloporphyrins were used. The rate of dioxygen uptake was determined with the aid of a gas buret and the amounts of peroxides and peracids were determined by titration with a Ce(IV) solution and a thiosulfate solution,8)4 respectively. From the results for the autoxidation of benzaldehyde in Table 9, the reaction conditions resulted in mostly thermal initiation and not photochemical initiation. The rates of dioxygen uptake were the same for blanks run at 300C in a lighted room and in a darkened room. 79 85 Zaikov and Cooper and Melville have previously found that the 61 Table 9 Rates of Dioxygen Uptakecfor the Autoxidation of Aldehydes at 30 C and 1 ATM 02 Aldehyde Catalyst mL min_1 Ratea PhCHO ----- 1.00b ---- 1.00° P1-C0-porCo(B) 1.63 6A0 P1-C0-porFeCl(B) 0.A0 185 TPP(COZEt)uCO 2.00 926 PrCHO ----- 0.80b -—-- P1-CO-porCO(B) 1.70 677 TPP(CO2Et)uCO 1.98 918 amL of dioxygen minn1mmole"1 M b . clight dark 62 thermal initiation of'autoxidation of aldehydes at 300C is significant. In the autoxidation of benzaldehyde and butanal, TPP(COZEt)uCo and P1-C0-porCo(B) showed a slight increase in the rate of dioxygen uptake relative to the unassisted blanks. When the rates for TPP(COZEt)uCo and .P1-CO-porCo(B) are calculated on a.mL min-1mmole of Co-1 basis, TPP(COZ- Et)uCo had an uptake of 926 mL of dioxygen min-1mmole of Co-1 and P1-CO- 1 porCo had 6A0 mL of dioxygen min-1mmole of Co- for the autoxidation of benzaldehyde. For butanal, the rates were 918 mL of dioxygen.min-1mmole of Co-1 and 667 mL of dioxygen min-1mmole of Co-1, respectively. P1-CO- porFeCl(B) retarded the autoxidation of benzaldehyde relative to the rates for the blank runs and had a rate of dioxygen uptake of only 185 mL of dioxygen min-1mmole of Fe-1. When the selectivity for the formation of the peracid is con- sidered, the autoxidation of benzaldehyde in the presence of P1-CO- porCo(B) showed a decrease from about 65% to nearly 30% over a 2 hour period. For butanal, the selectivity went from A0% to 75% over a,2 hour period for P1-CO-porCo(B) and remained at approximately 50% for TPP- (C02Et)uCo for at least 3 hours. Dee and coworkers observed that for the TPPCo-assisted and TTPCo-assisted autoxidations of acetaldehyde that the selectivity remained nearly constant for at least 3 hours at 801.82”83 In contrast, the metallated polyphthalocyanines were found to have selectivities which varied with time.80’83 As in the autoxidation of cyclohexene, the autoxidations of benz- aldehyde and butanal resulted in the bleaching of both P -C0-porCo(B) 1 and P1-C0-porFeCl(B) and of solutions of TPP(COZEt)uCo. Therefore, the porphyrin ring was decomposed during the autoxidations of benzaldehyde and butanal. 63 III. DISCUSSION A. Friedel-Crafts Acylation and Alkylation of Divinylbenzene- Polystyrene Copolymers. The Friedel-Crafts acylation of divinylbenzene-polystyrene copoly- mer beads (XAD—2 from Rohm and Haas) with TPP(COCl)uH2 and AlCl3 was first investigated by Rollmann.1u In his work, he indicated that the resulting porphyrin-containing polymer could be metallated, although elemental analysis indicated that the sample had a nitrogen to metal 5A This result may be compared ratio of 25 to 1 for the cobalt complex. with two other samples prepared by Rollmann.“4 When TPP(NH2)uH2 was attached to chloromethylated, divinylbenzene-polystyrene copolymer beads (again XAD-2), elemental analysis of its copper complex was found to have a nitrogen to copper ratio of 7 to 1 for one sample and 10 to 1 for another. Theoretically, a ratio of 8 to 1 is expected. From these results, it would appear that metallation is trustworthy but that the Friedel-Crafts acylation of divinylbenzene-polystyrene c0polymer beads which was catalyzed with AlCl3 has drawbacks which were not addressed in the original research. In this work, the Friedel—Crafts acylation and alkylation of 20% divinylbenzene-polystyrene copolymer beads was reinvestigated. Three serious drawbacks to these reactions became apparent. The low loadings associated with these reactions could not be circumvented. The nitrogen to metal ratio was again high as in the work of Rollmann.1u Lastly, the problem of aluminum contamination of the divinylbenzene-polystyrene copolymer beads was found. The latter two problems will be discussed at this point. 6A The high nitrogen to metal ratios found in this work and in Rollmann's for the acylation and alkylation reactions indicates an inherent weakness in these AlCl -catalyzed reactions. This is borne out 3 by Rollmann's results for his samples of Cu[Res-NH-TPP-NH2] with nitro- gen to copper ratios of 7 to 1 and 10 to 1 (theoretical 8 to 1) 1A In this work, P3-CH2-O-porCo had a nitrogen to cobalt ratio of 5 to 1 (theoretical A to 1). These results indicate that metallation of the polymer-bound porphyrins is not the problem. For P1-CO-porCo and P1- CH2-porCo, the nitrogen to cobalt ratios were 35 to 1 and 38 to 1, respectively. This would suggest that the porphyrin molecule is subject to some form of decomposition. This possibility of decomposition is supported by the complete decompostiion of TPP(COCl)uCu during the AlClB-catalyzed Friedel-Crafts acylation of 20% divinylbenzene-polysty- rene copolymer beads. When the ratios of nitrogen to metal are compared for Rollmann's 1A work and for this work, the ratios for this work are higher for P1-CO- porCo and P1-CH2-porCo than Rollmann's sample which is analogous to P1- CO-porCo. The higher temperatures which were used in this study may be responsible for this outcome. Thus far, it has been shown that AlCl3-catalyzed, Friedel—Crafts acylation and alkylation reactions result in the apparent decomposition of the porphyrin. It was also found that the beads were contaminated with aluminum. The question of where the aluminum resides in these porphyrin-containing cepolymer beads must be addressed at this point for the aluminum could be either present as an adduct with the phenyl groups of the copolymer or as an aluminum porphyrin. 65 Neckers has posted a warning which involves AlCl 55 3 and divinylben- It has been shown that AlCl3 forms a relatively stable chemical entity with 2% divinylbenzene-polystyrene 56 zene-polystyrene copolymers. copolymers. These AlCl -containing copolymers have been shown to 3 . 57 56 remain active as catalysts for acetal, 55 ester,55 and ether formation and transesterification for periods of at least one year. Further- more, washing of these samples with water, ether, acetone, hot isopro- panol and ether result in beads which contain as much as 3.7% A1.56 Therefore, Neckers has noted that considerable amounts of A1013 may persist after extensive washing of divinylbenzene-polystyrene copoly- mers which have come into contact with AlCl3. As mentioned, the other possibility for the location of the aluminum is that it could be present as an aluminum porphyrin. Once formed, aluminum porphyrins are known to be among some of the most 57 stable of metalloporphyrins. Therefore it would not be possible to exchange or remove the aluminum from the porphyrin-containing copoly- mers with any degree of certainty if it were present as the metallopor- phyrin. Aluminum can also displace many metals from their metalloporphyrin complexes. It has been shown that AlEt3 and diisobutylaluminum hydride can displace such metals as Cu(II), Fe(III), Zn(II), and Sn(IV)(OAc)2 from their octaethylporphyrin complexes58 and may indicate that AlCl3 could possibly have displaced some of the copper from TPP(CHZOH)uCu in the Friedel-Crafts alkylation of the c0polymer, P1. When AlCl3 is treated with TTPH2 in carbon disulfide, it formed TTPAlOH in a yield of only 16%. Therefore it is possible for A1013 to 66 react with a porphyrin in a solvent of low polarity to form an aluminum porphyrin. It can be seen that aluminum porphyrin formation is a possibility which could occur during AlCl -cata1yzed Friedel-Crafts 3 reactions. With this in mind, the infra-red spectra of P -CO-porCo and P -CH - 1 1 2 porCu were examined to determine which possibility for aluminum oc- curred. An absorption at 1650 cm-1 has been reported as being charac- teristic for AlClB-containing, 2% divinylbenzene-polystyrene copoly- mers.56 For P1-CO-porCo, a strong absorption is observed at 1680 to 16A0 cm-1. Since the carbonyl absorption has been reported by Roll- mann“I as being at 1670-1680 cm.1 and the absorption for the AlCl3 adduct at 1650 cm-1, it is not clear as to whether the absorption for P1-CO-porCo is a result of either the carbonyl and AlCl3 the carbonyl. For P1-CH2-porCu, the carbonyl absorption is not present to obscure the region. Unfortunately, the absorption spectrum for P1- adduct or just CHZ-porCu does notclearly show any absorption at or around 1650 cm-1. There may be a weak absorption present but it is of such intensity as to be unreliable for assignment. Since infra-red spectroscopy could not answer the question of the location of the aluminum, resonance raman spectroscopy was used to determine if aluminum porphyrins are present in these samples. Reso- nance raman spectroscopy of metalloporphyrins has shown promise in various structural studies. Babcock and coworkers have used this technique to probe the coordination sphere of iron porphyrins59 in an effort to better understand the coordination sphere in cytochrome oxidase. In addition, several metalloporphyrins other than iron 67 porphyrins have been investigated with resonance raman spectroscopy. Thus far, resonance raman spectra have been reported for at least TPPMnx,°° TPPCo,6O Cu porphine,°2 TPPNi,63 TPPCu,63 53 6A,65 and PdTPP. Other references are available. The use of resonance raman spectroscopy is attractive because of its sensitivity to changes in coordination. Samples of TTPCu and TTPAlOH in dichloromethane were prepared and used as standards for the resonance raman absorptions of these metallo- porphyrins. TTPCu was found to have four major absorptions at 1563, 1362, 1237, and 1076 cm"1 (Figure 21). TTPAlOH had absorptions at 15A9, 1 1378, 1259, and 12A2 cm- (Figure 22). The sample, P -CH -porCu, was 1 2 found to have absorptions at 1560, 1365, 1228, and 1077 cm-1 (Figure 23). This spectrum indicates that a copper porphyrin is present in the powdered copolymer. The base line of P1-CH2-porCu was found to fall over the region of 1710 to 1000 cm.1 and this was attributed to florescence. Due to the fall of the base line, it was not possible to determine if any aluminum porphyrins were present. Since infra-red and resonance raman spectroscopies were unable to locate the aluminum, another approach was used to determine if aluminum was incorporated into the porphyrin during the AlCl -catalyzed Friedel- 3 Crafts reactions. The Friedel-Crafts acylation of ethylbenzene with TPP(COCl),4H2 was investigated under similar reaction conditions. The reaction was carried out run in nitromethane at 50°C with the same ratio of reactants and solvent. After the reaction was completed, the product was esterified (at reflux) in 1-octanol with concentrated sulfuric acid added to catalyze 68 50 cm" L——-l 1600 1400 1200 Figure 21. Resonance Raman spectrum of TTPCu. 50 our! 1—————1 l L L 1600 1400 1200 Figure 22. Resonance Raman spectrum of TTPAlOH. 69 soafi' 1600 I400 IIOO Figure 23. Resonance Raman spectrum of Pl-CHZ-porCu. 70 the reaction. The resulting ester-containing porphyrin was then chro- matographed on alumina. The visible spectrum of each fraction appears ‘0: be that of a.free base porphyrin (Figure 2A). Protonation with trifluoroacetic acid, TFA, reveals that the free base porphyrin is the dominant or only porphyrinic species present for no major absorption at or near 550 nm was observable. This band would have been due to an aluminum complex of a meso-tetraarylporphyrin. The proton NMR spectrum of the first and principle fraction indicates that the ratio of octyl ester groups to ethylphenyl groups is approximately one to one which would mean that only about 50% of the available acid chloride groups were converted into diphenyl ketone groups (Figure 25). The 1H NMR spectrum also shows the presence of the -NH hydrogens. From the integration, their intensity is near what is expected when compared to the intensity of the B-hydrogens of the porphyrin periphery. This may indicate that little if any aluminum was present in this fraction. The remaining fractions consisted of verylittle material so no 1H NMR was taken for these. A second effort at the Friedel-Crafts acylation of ethylbenzene was made. This time the resulting product was washed with water and then methanol and dichloromethane. The methanol and dichloromethane soluble fractions were saved. The remaining solid was dissolved with aqueous potassium hydroxide (1N) and reprecipitated with the addition of acetic acid. This was repeated three times to free any aluminum ions from the porphyrins. Each of“ the1 resulting fractions, methanol, dichloromethane, and aqueous KOH, were found to contain free base porphyrins (Figures 26-28, respectively). The combined methanol and 71 l i 1 L 1 1 400 450 500 550 600 650 700 nm F1 e 2“. UV-VIS gur spectrum of TPP(C02octyl)u_x(COC6H4C2H5 x' TMS 001 ° 3 L 12 8 6 A 2 0 -9 DPT 1 F1 re 2 . H NMR P ‘ ' \ gu 5 1 spectrum of T P(Cozoctyl)u_x(CCC6RQC2H5)x. 72 v I 400 450 500 550 600 650 760 nm Figure 26. UV-VIS spectrum of methanol solution from TPP(COCl)nH2 + ethylbenzene. 1 1 L J 1 1 1 1 400 450 500 550 600 650 700 Figure 27' UV‘VIS Spectrum of dichloromethane solution nm from TPP(COCl)uH2 + ethylbenzene. 73 I I I I I l I w L 400 450 500 550 600 650 700 750 nm q - c Figure 2-. UV VIS spectrum of TPP(COZH)u-x(COC6HuC2H5)x in aqueous KOH. 7A dichloromethane fractions were then evaporated and treated 'with a solution of 30% H20 in acetic acid (1 to 2 volume ratio) at reflux for 2 three hours. The resulting solution was tested for the presence of aluminum ions. Aluminon (ammonium aurin tricarboxylate) was used to qualitatively test for aluminum. The test proved to be positive which indicates the presence of Al. Therefore aluminum can be incorporated into the porphyrin moiety during AlCl -catalyzed, Friedel-Crafts acyla- 3 tion. In conclusion, the AlCl3-catalyzed, Friedel—Crafts acylation and akylation of 20% divinylbenzene-polystyrene copolymer beads caused to some extent an apparent decomposition of the porphyrin and to also contaminate the copolymer with aluminum. It was found that contamina- tion still occurred for both reactions when TPP(COCl)uCu and TPP(CHZ- OH)uCu were used. Efforts to determine the location of aluminum in the copolymers were not successful. Through analogous Friedel-Crafts acylation of ethylbenzene with TPP(COCl)uH2, it is apparent that alumi- num can be incorporated into the porphyrin during AlCl -catalyzed 3 Friedel-Crafts acylations and alkylations. Therefore it is believed that the aluminum exists as an aluminum porphyrin in these samples and as an adduct with the 20% divinylbenzene-polystyrene copolymer beads. B. Scanning Electron Microprobe Analyses The results from the scanning electron microprobe analyses of metallOporphyrins bound In) 20% divinylbenzene-polystyrene copolymer beads show that the radial distribution of the metalloporphyrins varies from method to method used in the attachment. The distributions varied from high loadings at or near the surface to even loadings throughout. 75 A trend was noticed that the less reactive the functional group of the porphyrin was the more evenly distributed was the resulting bound porphyrin and its metal complex. SEM scans of P1-CO-porCo, P1-C5-O-porCo, P2-NH-C0-porCo, and P3- CHZ-O-porCu(B) were characterized by low values of Ic' These low values of Ic indicate that the penetration of the reactive porphyrin was poor for little porphyrin.managed to penetrate into the interior of the beads before reaction had occurred. These samples were prepared from reactive groups in the Friedel-Crafts acylation and alkylation, and amide forma- tion with TPP(COCl)uH2. For P3-CH2-O-porCu(B), reaction time is a more likely factor. For PZ-NH-CHZ-porCo, its SEM scan shows that the cobalt porphyrin is evenly distributed throughout the bead. This result indicates that the porphyrin had little difficulty in diffusing throughout the bead. Since PZ-NH-CO-porCo does have a low value of Ic’ the result for PZ-NH- CH2-porCo is useful in showing that relative reactivity of the porphy- rin's functional groups plays a significant role in determining the radial distribution of the polymer-bound metalloporphyrin on the bead. The results for P2-NH-CO-porCo and P2-NH-CH2-porCo show that the size of the porphyrin molecule is not the cause for the poor penetration of the porphyrins which was found for P -C0-porCo, P -C -O-porCo, and 1 1 5 Pz-NH-CO-porCo. Size would seem to be a poor reason, for 20% divinyl- benzene-polystyrene copolymer beads have pore sizes of approximately 1200 A. This was determined from photographs taken with an electron 37 microscope. Therefore size should not be the reason low values of Ic were obtained but reactivity does seem a pausible explanation. 76 In the case of the porphyrins attached to chloromethylated, 20% divinylbenzene-polystyrene copolymer beads, these samples were charac- terized with high values of Ic' For P3-CH2-0-porCo, P3-CH2-NH-porCu, and P -CH -py-porCu, the reactivity of the respective porphyrin's func- 3 2 tional group is less than that of a porphyrin like TPP(COCl)uH2. Therefore, these porphyrins were able to effectively diffuse throughout the copolymer before reacting with a chloromethyl group. In conclusion, the SEM data is able to show that the radial distributions of porphyrins and metalloporphyrins can be affected by the particular reaction which is used to couple the porphyrin to the 20% divinylbenzene-polystyrene copolymer beads. It was shown that the relative reactivity of the functional group had an effect on how well the porphyrin diffused through the 20% divinylbenzene-p0lystyrene co- polymers that were used. C. Electron Spin Resonance Analyses. When the ESR spectra of the polymer-bound copper porphyrins are considered in light of the results that were obtained from SEM analysis and elemental anlaysis, there are two noticable trends which affect the resolution of the ESR spectra of the polymer-bound copper porphyrins. The distribution and the amount of the copper porphyrin bound to the divinylbenzene-polystyrene copolymer beads play a significant role in determining the relative degree of resolution of the ESR spectrum for a particular sample. In those samples with less than 0.1% Cu such as P -CO-porCu, P - 1 1 CHZ-porCu, and P1-CH2-porCu(B), the copper ESR spectra are well re- solved with all but the nitrogen perpendicular superhyperfine lines 77 being observable at room temperature. For all but P1-CH2-porCo and P1- CHZ-porCu(B) for which no SEM data were obtained, the SEM data indicates that the bulk of the porphyrin was bound at or near the surface of the beads. These levels of loading near the surface did not have any effect on the resolution of the ESR spectra of these samples. PZ-NH-CO-porCu had a low value of lo and a copper content of 0.153%. When these numbers are taken together, there must be a considerable amount of cepper porphyrin molecules in a small volume of space. It is not surprising that the ESR spectrum of this complex is of such poor resolution. This lack of resolution may be due to the proximity of the copper porphyrin moieties. It has been shown by Barker and Stobart that in a polycrystalline sample of TPPCu that all of the nitrogen superhyperfine splittings were no longer observable at room temperature and at 770K.70 This is believed due to dipolar interactions between the nearest neighbors since dipolar interactions were said to be negligible at distances greater than 12 A. This result may be compared to the ESR spectra of copper octaethylporphyrin, copper meso-mononitro— octaethylporphyrin, capper> a,8-meso-dinitro-octaethylporphyrin, and coppera,y-meso-dinitrooctaethylporphyrin.71 The ESR spectra of these copper complexes were used to determine the equilibrium constants for dimerization. In comparing the spectrum of P -NH-C0-porCu to those in 2 the above cited literature, it became apparent that dimerization is not the main cause for the poor resolution but that dipolar interactions must be occurring between the polymer-bound cOpper porphyrins. It is these dipolar interactions which must be causing the poor resolution for the ESR spectrum of P -NH-CO-porCu. 2 78 This must also be true for P3-CH2-O-porCu(B). It had an Ic = 0.08 and a 0.238% copper content. This would again result in high local concentrations of copper porphyrin moieties. Its ESR spectrum is very similar to that of the above P2-NH-CO-porCu and therefore it is probably experiencing a considerable amount of dipolar interactions between neighboring copper porphyrin residues. In the case of the remaining polymer-bound cOpper complexes, the value of Ic for each is either near or at unity. These samples are all comprised of materials having a relatively even distribution of the copper porphyrin across the cross section of their respective copolymer beads. For P3-CH2-NH-porCu and P3-CH2-py-porCu with a cOpper content of 0.352% and 0.310% copper respectively, the ESR spectra of these com- plexes are perhaps the best resolved of all of the spectra for the polymer-bound copper porphyrins. It is apparent that the even radial distribution of these beads must effectively isolate the copper porphy- rin moieties from each other. This effective isolation then results in obtaining a well defined ESR spectrum for each of these samples. With P2-NH-CH2-porCu, the c0pper content is 0.393% and the resolu- tion of this complex is less than that of either of the two above complexes. This may reflect the slight increase of copper content but this increase should not affect the ESR spectrum as much as this. When the ESR spectrum of P3-CH2-O-porCu is considered, its degree of resolu- tion is qualitatively equal to or greater than that of P2-NH-CH2-POFCU even though P3-CH2-O-porCu has a copper content of 1.363% Cu. From the ESR spectrum of P3-CH2-O-porCu, it is evident that the increased content of copper does result in an increase of dipolar interactions between the 79 copper porphyrins bound to P3. This is reflected in the decrease of resolution for spectra from P3-CH2-0-porCu in comparison to spectra from P3-CH2-NH-porCu or P3-CH2-py-porCu. In an effort to observe at what concentration of copper that the dipolar interactions become significant, a series of dilutions of TTPCu in 'I'I‘PH2 were prepared. This series was prepared by the slow co- crystallization of TTPCu and TTPH2 from a solution of dichloromethane and methanol. Table 10 lists the % Cu of the prepared samples along with pertinent ESR parameters that were taken from the room temperature ESR spectra» In Figures 29 through 3A, the ESR spectra of the first six of the series are presented. In Figures 29 and 30, the ESR Spectra of Cu 1 and Cu 2 are presented and are very similar to that reported by Assour for polycrystalline 67 TPPCu in TPPH at either room temperature or 770K. From the data 2 listed, it is quite apparent that these spectra are in all respects comparable to Assour's spectrum for TPPCu in TPPHZ. For Cu 3, the presence of all of the characteristic features are observable (Figure 31). In addition, two sets of four additional lines are visible between the Cul| lines of m = -3/2 and -1/2 and m.= -1/2 and 1/2. These lines are also present in the ESR spectrum presented by 67 2. these "extra" lines is unknown. The most important feature of this Assour for polycrystalline samples of TPPCu in TPPH The origin of spectrum is that the resolution of the nitrogen superhyperfine splitting is no longer as sharp in the region of 3200 to 3500 gauss as in the previous samples, Cu 1 and Cu 2. Sample Cu 1 Cu 2 Cu 3 Cu A Cu 5 Cu 6 Cu 7 Cu 8 Cu 10 Cu 11 a. 1n gauss estimated Cu .086 .33 .79 .AA .00 .89 .85 .73 .3A .67 2. 2. 2. EH 177 177 177 .17A .17A .172 .171 .171 .16A .16A .053 80 Table 10 31 .0A9 .0A9 .0A9 .0A9 .050 .051 .053 .052 .052 C11“ 201 201 202 206 206 208 209 209 212 210 ESR Data for Dilutions of TTPCu in TTPH a 17.5 17.5 17.6 17.0 16.6 1A.3 1A.3 1A.2 IOO gauss 3400 gauss 1——-I M 11111 Figure 29. ESR spectrum of Cu 1. 3400 gauss 100 gauss |-——I I ’ I 1wa 111 8A With Cu A, the nitrogen perpendicular superhyperfine lines are no longer resolved and the "extra" lines are only barely observable in Figure 32. The ESR parameters can still be determined for gll, g1, Cu'l, Cu , and . The nitrogen superhyperfine structure in the region of 3200 to 3500 gauss is of much poorer resolution. This trend of poorer resolution of the nitrogen superhyperfine lines continues in the next sample, Cu 5. For this sample, the nitrogen superhyperfine lines are still observable but are of very poor resolu- tion (Figure 33). In the next sample, Cu 6, the nitrogen superhyperfine lines are no longer observed in Figure 3A. In the remaining samples, Cu 7 through Cu 11, the parallel components of the copper remain visible and there is only moderate changes in the region between 3200 and 3500 gauss. These spectra are in Appendix C. This series of spectra indicate that the dipolar interactions between neighboring TTPCu molecules increases with the increase of the concentration of TTPCu in TTPHZ. These interactions are first noticable at a copper content of 0.79% Cu. At this concentration, the interac- tions are still of very little consequence but are noticable when its spectrum is compared to the ESR spectra of the first two samples, Cu 1 and Cu 2. With the next sample, Cu A has a copper content of 1.AA% Cu and the resolution of the nitrogen superhyperfine lines in the region between 3200 and 3500 gauss are considerably affected by the dipolar interactions between the copper porphyrins present in the polycrystal- line samples. This is even more true for Cu 5 in which the nitrogen superhyperfine lines are very poorly resolved in comparison to the spectra of Cu 1 and Cu 2. At a copper content of 2.89%, Cu 6 no longer 85 3400 gauss I l00 gauss 1-——-1 Figure 32. ESR spectrum of Cu A. 86 3400 gauss l 100 gauss I , . Figure 33. ESR spectrum of Cu 5. 87 3400 gauss | 100 gauss 1————1 Figure 3A. ESR spectrum of Cu 6. 88 exhibits any nitrogen superhyperfine splitting what so ever. From these results, it is apparent that dipolar interactions start to affect the ESR spectra of copper meso-tetraarylporphyrins at a copper content of around 0.8% and that these interactions can totally eliminate the nitrogen superhyperfine lines from the spectra at about a copper content of 2.9% Cu. When the polymer-bound copper porphyrins are viewed in light of the results from the spectra for dilutions of TTPCu in TTPH it becomes 2, apparent that the polymer-bound copper porphyrins experience greater dipolar interactions than the copper content of these samples would seem to allow. For PZ-NH-CHZ-porCu, the relative resolution of its ESR spectrum is very similar to that of either Cu A or of Cu 5. This would mean that PZ-NH-CHZ-porCu (0.393% Cu) has an effective concentration on the polymer matrix of 1.A to 2.00% copper. In the case of P3-CH2—O- porCu (1.363% Cu), its ESR spectrum is very similar to sample Cu 5 with a content of 2.00% copper. For P2-NH-CO-porCu, this is true also but to an even greater extent. This sample has a copper content of only 0.153% yet its ESR spectrum is very similar to Cu 5's especially near 3200 to 3A00 gauss. This result is due to the low Ic value for this polymer- bound porphyrin. Its actual concentration is not known but that of the analogous P -NH-C0-porCo was determined with SEM analysis to be 1.16% at 2 the edge. This result may be low for SEM data in this concentration range is low when compared to data obtained from neutron activation analysis (see Table 2). These results suggest a larger effective concentration of porphyrin and metalloporphyrin on the polymer matrix. 89 This effect of apparently increased concentration of the polymer- bound porphyrins is the result of the polymer structure. Photographs of cross sections of 20% divinylbenzene-polystyrene copolymer beads were 37 In these photographs, the bead is taken with an electron microscope. made up of many small nodules which are fused together. In addition, the beads are porous with pore sizes of as much as 1200 A. The most likely place for the bound porphyrin is on the surface of these nodules and not deep into the nodule because of size constraints. Therefore the porphyrin moieties are viewed as lining the surfaces of these nodules which make up the bead and thus increasing its effective concentration because of the nodules' and pores' respective dead spaces which are not available for porphyrin binding. From the ESR data, it has been shown that the polymer-bound cOpper porphyrins have varying degrees of site-to-site isolation on the poly- mer matrix. The isolation of copper porphyrins by the polymer matrix was most effective in the samples which are of low loading and/or have even radial distributions of the metalloporphyrin across the copolymer beads. This was found to be true for P -CO-porCu, P1-CH -porCu, P -CH - 1 2 1 2 porCu(B), P3-CH2-NH-porCu, and P3-CH2-py-porCu. In the case of higher loadings but even radial distributions, intermediate isolation of the porphyrins was evident from the resolution of the ESR spectra of these complexes (PZ-NH-CHZ-porCu and P3-CH2-O-porCu). Lastly, the isolation of polymer-bound porphyrins and, in particular, the polymer-bound cop- per porphyrins is least for P -NH-CO-porH and P -CH2-O-porH2(B) and 2 2 3 their copper complexes. This was clearly seen from their ESR spectra. 90 D. Autoxidation of Cyclohexene When assisted by metalloporphyrins and polymer-bound metallo- porphyrins, the autoxidation of cyclohexene gave the expected products for the free radical autoxidation. In addition, the metalloporphyrins and polymer-bound metalloporphyrins experienced decomposition which resulted from free radicals attacking the porphyrin periphery. ‘When the rates of dioxygen uptake are compared for the homogeneous, soluble metalloporphyrins with those of the polymer-bound metalloporphyrins, the homogeneous, soluble metalloporphyrins have larger rates. Only when ground samples of the polymer-bound metalloporphyrins are used, are the rates of dioxygen uptake comparable to those of the homogeneous, soluble metalloporphyrins. Therefore no advantage is found for using polymer-bound metalloporphyrins as initiators in the autoxidation of cyclohexene instead of the homogeneous analogs. When the uptake of dioxygen for P -CH -O-porCo is compared with 3 2 that of P2-NH-CO-porCo, it is seen that its rate of dioxygen uptake is 3.5 times greater. This is surprising since TTPCo and TPP(COzhexyl)uCo had rates of 20A0 and 1900 mL of dioxygen min-1mmole of Co-1, respec- tively, when dissolved in cyclohexene. This would indicate that the electronegativity of the phenyl substituent should not affect the rate of dioxygen uptake as much as the difference for P -NH-CO-porCo and P - 2 3 CH2-0-porCo used in the assisted autoxidation of cyclohexene. Since PZ-NH-CO-porCo has a very low value of IC and PZ-NH-CO-porCu experienced considerable dipolar interactions between neighboring cop- per porphyrins, the proximity of the polymer-bound cobalt porphyrin moieties to each other is believed responsible for the low rate of 91 dioxygen uptake found for this polymer-bound cobalt porphyrin. If only diffusion of the substrate into the polymer matrix determined the rate 2-NH-CO-porCo should be more active than P3- CHZ-O-porCo because of the respective locations of the cobalt porphy- rins in the two samples. Since P3-CH2-O-porCo is more active than P2- NH-CO-porCo, the proximity of the cobalt porphyrin residues must be of dioxygen uptake, then P involved in such a way as to retard the autoxidation of cyclohexene. Two possibilities present themselves as reasons that the close proximity of the cobalt porphyrin moieties would retard the rate of autoxidation of cyclohexene. The formation of u-peroxo cobalt porphy- rin dimers is one possibility that should be considered, especially since LeDon has shown that the u—oxo iron(III) porphyrin dimer exists in copolymers consisting of 20% divinylbenzene, 5% aminostyrene, and 75% 32 styrene. The other possibility is that the substrate, cyclohexene, may be excluded from the 5th and/or 6th coordination site of the polymer-bound cobalt porphyrin by steric factors, which may arise from the polymer matrix or a neighboring porphyrin residue. Since oxidation of the u-peroxo cobalt porphyrin dimer results in the ESR active u—superoxodicobalt porphyrin dimer, attempts were made to oxidize any of the suspected u-peroxodicobalt porphyrin dimer with a trace of I and 1-methylimidazole in benzene. The ESR spectra of P -NH- 2 2 CO-porCo before and after treatment with I2 had very weak lines centered around g = 2.0. The linewidths are 15 gauss for the 12 to 1A line pattern. These lines have been found in other samples of the other polymer-bound cobalt porphyrins (Figure 35). Chang has reported an ESR 92 3300 gauss Figure 35. ESR spectrum of a suspected u-superoxo dicobalt porphyrin dimer. 93 spectrum for the Ll-superoxodicobalt complex of a cofacial diporphy- rin.78. The spectrum had linewidths of 10 gauss and g = 2.02A. In comparison to Chang's data, these lines may or may not be from a u- superoxo cobalt porphyrin dimer. Therefore, it is unclear why the rates of autoxidation of'cyclohexene varied so much for P2-NH-CO-porCo and P3- CH2-O-porCo. When the results of the autoxidation of cyclohexene are considered for the polymer-bound iron porphyrin, P3-CH2-O-porFeCl, and compared with those of TTPFeCl, the most striking difference between these iron complexes is that of the incubation period. At 60°C, TTPFeCl required little or no time before oxidation of cyclohexene started. .But when P - 3 CH2-O-porFeCl was used, it required a lengthy incubation period of at least 3 hours before any observable uptake of dioxygen had occurred. The short incubation time for TTPFeCl is very similar to Fuhrhop's finding for OEPFeCl at 60°07” 73'7“ 33 72 FuhrhOp, LeDon, and Paulson have observed that u-oxo dimers of iron(III) porphyrins did not need incubation periods even at room temperature whereas a complex such as OEPFeCl did (approximately 1 hour).73’7u These authors have unanimous- ly cited iron(III) porphyrin u-oxo dimers as being the active species in the initiation of the autoxidation of cyclohexene and other alkenes. For the polymer-bound iron(III) porphyrins, the long incubation time would suggest that the necessary formation of the u-oxo dimer was retarded by the copolymer matrix of P The once used beads had a 3. shortened incubation period of only 20 minutes, which would suggest that they contained some of the u-oxo dimer. Therefore the results with P - 3 CH2-O-porFeCl support Paulson, LeDon, and Fuhrhop in that the u—oxo 91! dimer is indeed the active Species in the autoxidation of cyclohexene. The lengthy incubation time for P3-CH2—O—porFeCl indicates that the iron porphyrins are relatively isolated from each other in this sample. Yet the isolation is imperfect for the formation of the‘u-oxo dimer must have occurred for used beads have a shorter incubation period. E. Autoxidation of Aldehydes. From the results for the autoxidation of benzaldehyde and butanal, little improvement is observed for the dioxygen uptake rates for the cobalt porphyrin-assisted autoxidation of aldehydes relative to the unassisted autoxidation. In addition, TPP(COZEt)uCo is more active than its polymer—bound analog, P1-CO-porCo(B). Furthermore, P1-CO- porFeCl(B) retards the uptake of dioxygen. The selectivity of the polymer-bound metalloporphyrins offers no improvement over that of soluble cobalt porphyrins. Finally, the decomposition of the porphyrin ring for the complexes studied indicates that the effort to attach porphyrins to the polymer support is wasted. Therefore no benefit is gained in the attachment of metalloporphyrins to polymer supports and these polymer-bound metalloporphyrins being used in free radical autox- idation reactions. IV. CONCLUSIONS It has been shown that porphyrins may be covalently attached to divinylbenzene-polystyrene copolymers. The Friedel-Crafts acylation and alkylation of 2% and 20% divinylbenzene-polystyrene copolymer beads were studied. The use of aminated, 8% and 20% divinylbenzene-polysty- rene copolymer beads in the formation of amide and amine linkages were investigated as another means of effecting attachment. Finally chloro- methylated, 20% divinylbenzene-polystyrene cOpolymer beads were used in the formation of ether, amine, and pyridinium linkages to porphyrins. In the case of .AlC13-catalyzed Friedel-Crafts acylations and alkylations, two problems are found which may seriously limit the utility of these reactions. Aluminum contamination of the copolymer samples had occurred and efforts to pinpoint its location were not entirely successful. In the Friedel-Crafts acylation of ethylbenzene, aluminum had incorporated into the porphyrin ring in a small amount of the sample. Infra-red spectral analysis showed what might have been the A1013 adduct of the 20% divinylbenzene-polystyrene copolymer. There- fore the aluminum is believed to be present as an aluminum porphyrin and as an adduct with the copolymer. In addition, the other problem is that of high nitrogen to metal ratios for these samples which suggests that the porphyrin moiety has experienced some form of decomposition during the AlCl3-catalyzed reactions. 95 96 Aminated, 20% divinylbenzene-polystyrene copolymer beads were used as the solid support for the formation of amine- and amide-linked porphyrins. For TPP(COCl)uH2 coupling with P it was found that the 2’ resulting polymer—bound porphyrin and its metallated complexes had a very high loading at and near the surface of the beads. ESR spectra of its copper complex indicated that the porphyrin units are relatively close to each other, and causes the poor resolution of the nitrogen superhyperfine lines. The decrease in resolution has been shown to 70 arise from dipolar interactions. The proximity of the cobalt porphy— rin units has been suggested as a cause for the reduced rate of autoxidation of cyclohexene relative to that found for P3-CH2-O-porCo. In the case of Pz-NH-CHZ-porHZ, it has been determined that the re- sulting polymer-bound porphyrin and its metallated complexes are evenly distributed in the interior of the copolymer beads. This result indicated that diffusion of the porphyrin molecule is not restricted to as large an extent as might be suggested from the distribution found in PZ-NH-CO-porCo. The ESR spectra of P2-NH-CH2-porCu are much better resolved than those of PZ-NH-CO-porCu and is true even though it has a greater loading per gram of beads than does P -NH-CO-porCu. From the 2 results of SEM analysis, this is not surprising for P -NH-CO-porCu 2 contains most of its copper porphyrin residues at or near the surface of the beads which results in greater dipolar interactions. From the SEM analysis and ESR analysis, these results clearly show that the reactivi- ty of the functional group of the porphyrin plays a role in determining the distribution of the metalloporphyrins along the radii of the beads. 97 For chloromethylated, 20% divinylbenzene-polystyrene c0polymer beads, P3, it was found that high and uniform loadings were possible. These samples gave some of the best resolved copper ESR spectra for their copper complexes. In comparison to the other methods of attach- ment of'porphyrins to divinylbenzene-polystyrene copolymers, the use of P3 as the solid support is preferred. The ease of the substitution reaction and the quality of the resulting polymer-bound porphyrins and their metallated complexes makes these beads, P3, as the preferred choice as starting material for the polymer support for the covalent attachment of porphyrins. The ESR spectra of the polymer-bound vanadyl and copper complexes show the presence of these complexes attached to divinylbenzene-poly- styrene copolymers. These spectra clearly show the result of immobili- zation of the metalloporphyrin on the copolymer matrix because the spectra resemble spectra of polycrystalline TPPCu in TPPH or TPPCu in 2 CHCl3 at 770K.67 When the ESR spectra of the polymer-bound copper complexes were compared with those of a series of TTPCu in TTPH2 dilutions, it was shown that the polymer-bound copper porphyrins exper- ienced greater dipolar interactions than might be expected from the concentration of copper in many of the samples. When these results were coupled with those of SEM analysis, it became apparent that the radial distribution and the average loading had an affect on the resolution of the nitrogen superhyperfine splitting. Resonance raman spectroscopy showed that copper porphyrins were present in P1-CH2-porCu(B). Therefore this technique of analysis could be very useful as a companion to ESR spectroscopy in the analysis of 98 metalloporphyrins bound to polymers. It would be especially useful for the analysis of those polymer-bound metalloporphyrins which do not have ESR signals. It was found that the polymer-bound cobalt porphyrins are not as effective as the analogous soluble cobalt porphyrins are as catalysts for the autoxidation of cyclohexene or of aldehydes. In these autoxida- tions, the cobalt porphyrins were susceptible to decomposition. In the case of P3-CH2-0-porFeCl, it required an extended incubation period before the uptake of dioxygen began in the autoxidation of cyclohexene. 33 This result supports the findings of Paulson,72 LeDon, and Fuhrhop73’7n that the u-oxo dimer must be present before the autoxida- tion of cyclohexene can be initiated. The polymer-bound iron complex also underwent decomposition during the autoxidation of cyclohexene as .did TTPFeCl. Therefore, since reactivity is lower for the polymer-bound metalloporphyrins and they do undergo decomposition during these free radical chain reactions, their use as catalysts for autoxidation reac- tions would not seem advisable. V. EXPERIMENTAL A. Materials. Macrorecticular, divinylbenzene-polystyrene copolymer beads were gifts from the Dow Chemical Company. The divinylbenzene content of those beads which were used are 2%, 8%, and 20% divinylbenzene. Chloro- methylated, 201 divinylbenzene-polystyrene copolymer beads were pur- chased from Strem Chemical Company. The aldehydes which were used to synthesize the meso-tetraarylporphyrins were obtained from Aldrich and were used as received. The bulk of reagents and solvents which were used were reagent grade and were used as is. The exceptions are that tetrahydrofuran and cyclohexene were distilled from over sodium. B. Preparation of Divinylbenzene-Polystyrene Copolymer Beads. Prior to their use, divinylbenzene-polystyrene copolymer beads were sieved through screens. Beads (28-32 mesh) were used for all further work. These were then washed with the following solvents: 10% aqueous hydrochloric acid (V:V), 10% aqueous sodium hydroxide (W:W), water, 1:1, water/methanol (V:V), methanol, 1:1, methanol/dichloro- methane (V:V), and dichloromethane. The beads were dried overnight in a vaccuum at 0.1 mm of Hg and 50°C. 99 100 C. Preparation of Aminated, Divinylbenzene-Polystyrene Copolymer Beads. The procedure of King and Sweet20 was used in the nitration of divinylbenzene-polystyrene copolymer beads. Below the nitration and reduction with stannous chloride is described for 20% divinylbenzene- polystyrene copolymer beads. 1. Preparation of Aminated, 20% Divinylbenzene-Polystyrene Copolymer Beads. Acetic anhydride (39 mL) was added to 10 g of beads in a 100 mL round bottom flask. This mixture was cooled to 5°C by immersion in an ice water bath before the addition of a solution of 3.1 mL of 70% nitric acid in 8.5 mL of acetic acid. This mixture was allowed to warm to room temperature after 30 min. of stirring at 5°C. The reaction was stopped after a total of 5 h. The solvents were then removed by suction. The resulting beads were then washed 5 times for 15 min. each with 20 mL of acetic acid. The still wet beads were stirred at 40°C for 3 days with #0 mL of acetic acid and a solution of 11.0 g of stannous chloride dihydrate in 12 mL of concentrated hydrochloric acid. The solution was again removed by suction and the beads were then washed as follows: 5 times with a 3:10 mixture of concentrated hydrochloric acid and acetic acid, 3 times with 3:5:5 hydrochloric acid/tetrahydro- furan/methanol, and 2 times with methanol. These beads were dried at 25°C and 0.1 mm of Hg overnight. A 2.0 g batch of these beads was then washed twice for 20 min each with a 10% KOH in methanol solution and then five times with methanol and twice with dichloromethane. The beads were dried at 60°C (0.1 mm 101 Hg) for 4 h. Nitrogen content of the beads was 3.83%. Before reduction nitro absorptions were observed at 1520 cm-1 and 13N6 cm-1 in the nujol mull of ground and nitrated, 20% divinylbenzene- polystyrene copolymer beads. After reduction, these peaks were reduced in intensity with only the one at 13H6 cm"1 being easily observed. In addition, the ammonium chloride salt absorptions were observed at 2600 cm-1 and 2000 cm-1. 2. Preparation of Aminated, 8% Divinylbenzene-Polystyrene Copolymer Beads. In the case of 8% divinylbenzene-polystyrene copolymer beads, nitration and reduction of the nitro groups as above resulted in a copolymer which was susceptible to pulverization. Therefore these beads were not studied any further. D. Preparation of Porphyrins and Metalloporphyrins. The porphyrins were synthesized from pyrrole and appropriately substituted benzaldehydes in refluxing propionic acid. The procedures ua,u9 50 of Adler and of Little were used to prepare the desired porphy- rins. The metalloporphyrins were primarily prepared in a refluxing DMF solution of the porphyrin and the desired metal salt.51 1. 5,10,15,20-Tetrakis(4-methylphenyl)porphyrin, TTPHZ. Para-tolylaldehyde (12.0 g) and pyrrole (6.7 g) were added to hot propionic acid (500 mL) and the resulting solution was refluxed for 0.5 h. The solution was allowed to cool and sit overnight before the crystals were collected by filtration. The crystals were then washed with methanol until the washings were colorless. The crude porphyrin was purified by chromatography (alumina/dichloromethane) and 102 recrystallized by the addition of’methanol to a concentrated solution of the porphyrin. The yields were typically 3.5 to 9.6 g (20-27% yields); NMR (CDC13),6, -2.79(s, 2H, NH), 2.69(s, 12H, -CH3), 7.53(d, 8H, tolyl- 3,5-protons), 8.08(d, 8H, tolyl-2,6-protons), 8.84(s, B-pyrrole PD; A max (dichloromethane) 920, 486 sh, 518, 55“, 59A, 650 nm. Analysis performed on TTPCu. Calculated for C48H36NuCu: C, 78.52; H, 4.91; N, 7.63; Cu, 8.99. Found C, 77.93; H, “.93; N, 7.21; Cu, 9.93. 2. 5,10,15,20-Tetrakis(N-methylphenyl)porphyrinatocopper- (II), TTPCu. TTPH2 (0.30 g) and Cu(0Ac)2'H20 (0.30 g) were mixed together in 30 mL of DMF and then the mixture was refluxed for 30 min. Water (20 mL) was added to the reaction solution after it had cooled down to about 100°C. The copper porphyrin was collected by filtration next day and washed with water. After air drying, TTPCu was chromatographed (alumina/dichloromethane) and recrystallized from dichloromethane and methanol. Analysis. Calculated for Cu8H36NuCu: C, 78.52; H, 9.91; N, 7.63; Cu, 8.94. Found c, 77.93; H, n.93; N, 7.21; Cu, 9.93. A max (dichloromethane) 417, 5N1, 575 sh nm. 3. 5,10,15,20-Tetrakis(u-methylphenyl)porphyrinatocobalt- (II), TTPCo. TTPH2 (0.50 g) and CoC12'6H20 (0.50 g) were mixed together in 50 mL of DMF. The resulting mixture was refluxed for 30 min and then allowed to cool to approximately 100°C before 30 mL of water was added. The cobalt complex was collected by filtration and washed with water. After air drying, the cobalt porphyrin was chromatographed (alumina/di- chloromethane) and recrystallized from dichloromethane and methanol. 103 Analysis. Calculated for C48H36N4CO: C, 79.22; H, 4.99; N, 7.70; Co, 8.09. Found C, 80.86; H, 5.34; N, 7.38; Co, 8.41. Amax (dichloro- methane) 410, 528, 590 sh nm. 4. Chloro-5,10,15,20-Tetrakis(4—methylphenyl)porphyrinato- iron(III), TTPFeCl. TTPH2 (0.10 g) and FeCl2 (0.10 g) were mixed together in 25 mL of DMF and the mixture was then refluxed for 20 min. Water (25 mL) was added to the solution after it had cooled to about 100°C. The iron porphyrin was collected by filtration and washed with water. TTPFeCl was recrystallized from dichloromethane. Analysis. Calculated for C48H36N4F601: C, 75.84; H, 4.77; N, 7.37; Fe, 7.35; Cl, 4.66. Found C, 77.19; H, 5.03; N, 7.42; Fe, 6.23; Cl, 4.13. 5. Hydroxo-5,10,15,20-Tetrakis(4—methylphenyl)porphyrinato- aluminum(III), TTPAlOH. a. TTPH (0.30 g) was suspended in 200 mL of carbon 2 disulfide at room temperature.86 AlCl3 (3.5 g) was added in small portions over a 5 min period and the resulting mixture was stirred for another 25 min. The carbon disulfide was then removed at reduced pressure. The residue was dissolved into dichloromethane and chromato- graphed (alumina/dichloromethane). The first band eluted was TTPH2 and the second band contained TTPAlOH which required 2% methanol in di- chloromethane to elute the aluminum porphyrin. Yield 11 mg or 16.0%. Amax 417, 508, 549, 589 nm. TTPAlOH has a resonance raman, metal- sensitive absorption at 1549 cm-1 when it is excited with a laser of 413.1 nm. b. TTPH2 (150 mg) and AlCl (150 mg) were mixed together 3 in 20 mL of nitromethane and the mixture was stirred at 50°C for 24 h. 104 for 24 h. The mixture was poured into 50 mL of water and the porphyrin was extracted into dichloromethane. The green solution was neutral- lized with 0.1 N aqueous KOH. The porphyrin was chromatographed (alumina/dichloromethane) and only one band was found. This band contained only TTPH No TTPAlOH was found. 2. 6. 5,10,15,20-Tetrakis(4-carbohexylphenyl)porphyrin, TPP- (C02hexyl)uH2. 4-Carboxybenzaldehyde (5 8) was added to 335 mL of propionic acid and then pyrrole (2.23 g) was added to the hot solution. After refluxing for 0.5 h, the reaction solution was allowed to cool and sit overnight. The crude porphyrin was collected by filtration and washed with hot water. The crude porphyrin was then dissolved in aqueous NaOH and precipitated by the addition of acetic acid (pH 3). The porphyrin was again collected by filtration and washed with water. Thus treated, the porphyrin was dried at 120°C overnight ( 35% yield). Conversion to the tetrahexyl ester was performed to increase the solubility and to facilitate the purification of the porphyrin. This was accomplished when 4.0 g of the crude porphyrin tetra acid was treated with 100 mL of a 10% H2804 in hexanol solution (V/V). The solution was refluxed for 24 h and then diluted with 300 mL of H20 and extracted with dichloromethane. The dichloromethane fraction was washed with saturated sodium bicarbonate solution and then concentrated on a rotary evaporator. An equal volume of methanol was then added to the solution. to crystallize the porphyrin tetrahexyl, ester. The porphyrin tetrahexyl ester was chromatographed (alumina/dichloromethane) and recrystallized from dichloromethane and methanol. Yield from pyrrole was 17%; NMR (CDC13),<5, -2.79(2, 2H, NH), 105 0.96(t, -CH3), 1.42(m, 2H, -CH2-), 1.58(m, 2H, -CH2-CH3), 1.92(m, 2H, - O-CHZ-CH2-), 4.51(t, 2H, 0-CH2-), 8.29(d, 8H, tolyl-3,5-protons), 8.45(d 8H, tolyl-2,6-protons), 8.83(s, B-pyrrole H); Xmax(dichloro- methane) 420, 488 sh, 518, 552, 592, 647 nm. Analysis performed on cobalt complex. Calculated for C72H72Nu08Co: C, 72.65; H, 6.42; N, 4.73; 0, 10.82; Co, 4.98. Found: C, 72.93; H, 6.46; N, 4.61; 0, 10.76; Co, 5.24. 7. 5,10,15,20-Tetrakis(4-carboethylphenyl)porphyrinato- cobalt(II), TPP(COZEt)uCo. 5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrin (200 mg) 'was treated with a solution of 1 mL of H2804 in 50 mL of ethanol. The resulting solution was then refluxed for 36 h. The solution was neutrallized with aqueous sodium bicarbonate and the porphyrin tetra- ester extracted with dichloromethane. The dichloromethane was removed at reduced pressure and the porphyrin was then treated with 0.2 g of CoCl2 6H20 and 10 mL of DMF. The solution was then refluxed for 3 h and after cooling fiSnfl.of water was added. The precipitated cobalt complex was collected by filtration and air dried. The crude cobalt porphyrin was then chromatographed (alumina/dichloromethane) and recrystallized from dichloromethane and methanol. Xmax (dichloromethane) 414, 532 nm. 8. 5,10,15,20-Tetrakis(4-carbohexylphenyl)porphyrinato- cobalt(II), TPP(COZhexyl)uCo. TPP(COZhexyl)uH2 (1.0 g) and CoClZ'6H20 (1.0 g) were mixed together in 100 mL of DMF and heated to reflux. After 45 min, the reaction solution was allowed to cool to approximately 100°C before 75 106 mL of H20 was added to the solution. The cobalt porphyrin was collected by filtration and air dried before it was chromatographed twice (once alumina/dichloromethane and then silica gel/dichloromethane) and then recrystallized from dichloromethane and methanol. Analysis. Calcula- ted for C N408Co: C, 72.65; H, 6.42; N, 4.73; O, 10.82; Co, 4.98. 72H72 Found: C, 72.93; H, 6.46; N, 4.61; O, 10.76; Co, 5.24. Amax (dichloro- methane) 414, 532 nm. 9. 5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrin, TPP(C02- H)uH2. TPP(COZhexyl)uH2 (0.4 g) and KOH (0.8 g) were mixed together in 100 mL of THF and 20 mL of water. The resulting solution was refluxed for 24 h. The THF was removed at reduced pressure and then 3 mL of acetic acid was added to the aqueous solution. The precipitated porphyrin was collected by filtration, and. washed extensively' with water. After initial drying in air, the porphyrin was dried for 5 h in an oven at 140°C. Amax (ethanol) 415, 478 sh, 513, 547, 590, 646 nm. 10. 5-(4-Hydroxyphenyl)-10,15,20-tris(4-methylphenyl)por- phyrin, T3P(OH)H2. Para-hydroxybenzaldehyde (4.6 g) and para-tolylaldehyde (13.5 g) were added to 500 mL of hot propionic acid. Pyrrole (10.1 g) was then added and the reaction mixture was refluxed for 1 h. After cooling and standing overnight, the crude porphyrins were collected by filtration and washed with methanol until the filtrate was colorless. The porphy- rins were separated by chromatography. The first time alumina/di- chloromethane were used. The first band contained TTPH and the second 2 band contained T3P(0H)H2. The second band was rechromatographed on 107 silica gel with dichloromethane as elutent. Yield of TTPH2 was 1.69 g or 6.7% and the yield of T3P(0H)H2 was 1.65 g or 6.5%. NMR(CDC13), 6 , - 2.75(s, 2H, NH), 2.68(s, 9H, -CH3), 7.18 (m, 2H), 7.55(d, 6H, tolyl-3,5- protons), 8.05 (m, 2H), 8.09(d, 6H, tolyl-2,6-protons), 8.85 (s, 8H, 8- pyrrole H); Amax (dichloromethane) 421, 486sh, 519, 554, 594, 650 nm. 11. 5-(2-(5-Bromopentoxy)phenyl)-10,15,20-tris(4-methyl- phenyl)porphyrin, T3P(OCSBr)H2. 2-Hydroxybenzaldehyde (4.6 g) was used in place of 4-hydroxy- benzaldehyde. All other details were the same as in the preparation of T3P(0H)H2. Yield of TTPH2 was 1.92 g or 7.6% and that of the mono- hydroxyporphyrin was 0.55 g or 2.2%. Amax (dichloromethane) 420, 485 sh, 516, 552, 591, 650 nm. The porphyrin (0.55 g) was then treated with 4.6 g of 1,5- dibromopentane and 3.0 g of K2C03 in 100 mL of DMF. The resulting mixture was stirred for 2 days at room temperature in a nitrogen atmosphere. The reaction mixture was then poured into 500 mL of water and extracted into dichloromethane. The solution was concentrated and then chromatographed (alumina/dichloromethane). The porphyrin *mas recrystallized from dichloromethane and methanol. The yield of the porphyrin was 0.65 g (92% yield). NMR(CDCl3), 6 , -2.82(s, 2H, NH), 0.88(m, 6H, —CH -CH -CH2-), 2.20(t, 2H, CH 2 2 2 3.80(t, -O-CH2-), 7.47m, 6H, tolyl-3,5-protons), 8.02(d, 6H, tolyl- 'Br'), 2.63(S, 9H, “CI-13), 2,6-protons), 7.23(nn 4H, 3,4,5,6-protons), 8.71(s, 8H, 8—pyrrole); Amax (dichloromethane) 420, 485 sh, 518, 552, 594, and 651 nm. 108 12. 5-(4-Pyridyl)-10,15,20-tris(4—methylphenyl)porphyrin, T3P(py)H2. 4-Pyridinecarboxyaldehyde (4.3 g) and para-tolylaldehyde (13.9 g) were mixed together in 500 mL of propionic acid. Pyrrole (10.7 g) was then added to the hot solution and the reaction mixture was refluxed for 1 h. The reaction mixture was then allowed to stand overnight before collecting the crude porphyrins by filtration. They were washed with methanol until the washings were colorless. The porphyrins were chromatographed on alumina with dichloromethane as the solvent. The first band contained TTPH2 and the second band contained the desired porphyrin. The second band was then chromatographed on silica gel with dichloromethane as solvent. The yield of TTPH was 2.75 2 g or 10.2% and that of T3P(py)H2 was 1.05 g or 4.0%. Analysis. Calculated for Cu6H33N5Cu: C, 76.60; H, 4.58; N, 9.71; Cu, 9.10. Found: C, 75.75; H, 4.87; N, 9.62; Cu, 10.76. NMR(CDC13), 6, -2.80(s, 2H, NH), 2.69(s, 9H, -CH ), 7.54(d, 6H, tolyl-3,5-protons), 8.08(d, 6H, 3 tolyl-2,6-protons), 8.77(d, 2H, pyridyl-3,5—protons), 9.01(d, 2H, pyridyl-2,6-protons), 8.71(s, 8H, B-pyrrole). Amax (dichloromethane) 419, 486 sh, 518, 553, 592, 648 nm. 13. 5-(4-Pyridyl)-10,15,20-tris(4-methylphenyl)porphyrin- atocopper(II), T3P(py)Cu. T3P(py)H2 (60 mg) was treated with 60 mg of Cu(OAc)2°H20 in 20 mL of DMF at reflux for 30 min. Water (20 mL) was added after the solution had cooled for 10 min. The precipitated copper porphyrin was collected by filtration and allowed to air dry. T3P(py)Cu was then chromatographed (alumina/dichloromethane) and recrystallized from 109 dichloromethane and methanol. Amax (dichloromethane) 416, 541, 574 sh nm. Analysis. Calculated for Cu6H33N5Cu: C, 76.60; H, 4.58; N, 9.71; Cu, 9.10. Found: C, 75.75; H, 4.87; N, 9.62; Cu, 10.76. 14. 5-(4-Acetamidophenyl)-10,15,20-tris(4-methylphenyl)por- phyrin, T3P(NHAc)H2. Para-acetamidobenzaldehyde (8.2 g) and para-tolylaldehyde (18.2 g) were mixed together in 500 mL of hot propionic acid. Pyrrole (13.4 g) was then added to the hot solution and the solution was refluxed for 0.5 h. The reaction mixture was then refrigerated over- night and next morning the crude porphyrins were collected by filtration and washed extensively with methanol. The porphyrins were chromato- graphed on silica gel with dichloromethane as solvent. The first band contained TTPHZ. The second band was eluted from the column with 1% methanol in dichloromethane. The second band was rechromatographed as before and then recrystallized from dichloromethane and methanol. The yield of TTPH was 1.1 g and 4.3%. The yield of T3P(NHAc)H2 was 0.80 g 2 and 2.2%. NMR(CD013), 5, -2.80(s, 2H, NH), 2.31(s, 3H, C0-CH3), 2.68(s, 9H, -CH3), 7.53(d, 6H, tolyl-3,5-protons), 8.09(d, 6H, tolyl-2,6-pro- tons), 7.3, 7.8(m, 4H, phenylacetamide), 8.82(s, 8H, B-pyrrole). Amax (dichloromethane) 420, 487 sh, 519, 555, 594, 649 nm. 15. 5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrinatocopper- (II), TPP(COZH)uCu. TTP(C02H),4H2 (0.30 g) and Cu(OAc)2-H 0 (0.30 g) were mixed 2 together in 30 mL of DMF and the mixture was refluxed for 3 h. After the solution cooled to about 100°C, waster (20 mL) was added to precipitate 110 the copper porphyrin. Next day, it was collected by filtration and air dried. Xmax (aq. KOH) 413, 545, 580 sh nm. 16. 5,10,15,20-Tetrakis(4-hydroxymethylphenyl)porphyrin, TPP(CH20H)uH2. To a suspension of 0.56 g of lithium aluminum hydride in 50 mL of THF was added dropwise (30 min) a solution of 0.50 g of TPP(C02- hexyl)uH2 in 150 mL of'THF.52 After addition was completed, the mixture was refluxed for 1 h before adding an additional 100 mL of THF to the mixture. The reaction was continued at reflux for 0.5 h more before the reaction was allowed to cool to room temperature. Wet THF was then slowly added to the reaction mixture. After the complete decomposition of the excess LAH, the solution was then filtered through Whatman No. 1 filter paper. The THF was removed at reduced pressure on a rotary evaporator. The crude porphyrin crystallized from the remaining water and after collection by filtration, the crude porphyrin was washed with acetone. The porphyrin was recrystallized from pyridine and acetone. Yield of the porphyrin was 300 mg or 92.0% yield. Analysis. Calculated for c48H36N4O4CU: C, 72.39; H, 4.56; N, 7.04; 0, 8.04; Cu, 7.98. Found: C, 72.05; H, 4.88; N, 7.03; 0, 7.94; Cu, 8.10. I.R. spectrum had no absorption at 1680 cm-1 for ester. 17. 5,10,15,20-Tetrakis(4-hydroxymethylphenyl)porphyrinato- copper(II), TPP(CHZOH)uCu. Cu(OAc)20H20 (0,5 g) was added to a solution of 100 mg of TPP(CHZOH),,H2 in 50 mL of pyridine and 100 mL of THF. The solution was then refluxed for 2 h before the THF was removed at reduced pressure. 111 Water (50 mL) was added to the pyridine solution. The cOpper porphyrin crystallized overnight and was collected by filtration. The copper porphyrin was recrystallized from pyridine and acetone and was col- lected by filtration and washed with acetone. The sample was first air dried and then dried overnight at 25°C and 0.1 mm of Hg. Yield was quantitative. Analysis. Calculated for C48H36N4O4cu: C, 72.39; H, 4.56; N, 7.04; 0, 8.04; Cu, 7.98. Found: C, 72.05; H, 4.88; N, 7.03; 0, 7.94; Cu, 8.10. Amax (THF) 418, 541, 578 sh nm. 18. Attempted Synthesis of 5,10,15,20-Tetrakis(4-chloro- methylphenyl)porphyrin, TPP(CH2C1)uH2. a. To 100 mg of TTP(CH20H),4H2 in 20 mL of THF:pyridine (1:1) at 0°C was added dropwise thionyl chloride (0.5 mL). After the thionyl chloride was added, the ice bath was removed. After 3 11 at ambient temperatures, the reaction was stopped with the removal of excess thionyl chloride and solvents at reduced pressures. The product was then chromatographed (alumina/dichloromethane). Most of the por- phyrin remained at the top of the column. NMR of the product indicated that the product was partially chlorinated. NMR(CDC13),6 , -2.81(s, NH), 4.94(s, X-CHZ-Ph), 7.54 and 8.08(d, phenyl protons), 7.76 and 8.19(d, phenyl protons), 8.88(s, B-pyrrole). b. TTP(CH20H),‘,H2 (60 mg) was treated with 10 mL of thionyl chloride at ambient temperatures for 12 h. The excess thionyl chloride was removed as before. The product was chromatographed as before and the bulk of the porphyrin remained at the top of the column. NMR again showed a mixture. 112 c. TPP(CHZOH),4H2 (150 mg) was was treated with 10 mL of thionyl chloride at reflux for 24 h. ‘The resulting product was chromatographed as before but most of the porphyrin was eluted. NMR of the product showed that B—pyrrole substitution must have occurred for in place of the usual singlet were two broad multiplets at 8.6 and 8.9. d. TPP(CHZOHMH2 (40 mg) and triphenylphosphine (150 53 and 10 mL of mg) were mixed together in 10 mL of carbon tetrachloride THF. The resulting mixture was refluxed for 12 h. The solvents were removed and the porphyrins were chromatographed as before with the bulk remaining at the top of the column. NMR again showed partial chlorina- tion. 19. Friedel-Crafts Acylation of Ethylbenzene with TPP(COCl)uH2. Ethylbenzene (1.00 g) and nitromethane (10 mL) were added to TTP(C0C1),4H2 which had been prepared from 150 mg of TPP(COZH)uH2 and thionyl chloride. Then AlCl3 (150 mg) was added to the solution and the reaction was stirred at 500C for 24 h. The reaction mixture was poured into 50 mL of cold water and 100 mL of ethanol and stirred for 1 h. The crude porphyrin was collected by filtration and allowed to air dry. Workups are as follows: a. The crude porphyrins were heated at 120°C for 14 h in 25 mL of 1-octanol to which 2 mL of concentrated sulfuric acid had been added. The solution was allowed to cool before a solution of'methanolic sodium hydroxide was added. The resulting solution was poured into 50 mL of water and then the octanol layer was separated from the aqueous layer. The octanol layer was placed on top of a column of silica gel. 113 The column was eluted with pentane to remove some of the octanol. Next THF was used and then toluene. THF eluted the first and major band. Toluene eluted a wide band. The uv-visible spectra of these bands are identical with maxima at 419, 519, 553, 594, and 648 nm. NMR(CDC13), 6, -2.80(s, NH), 0.89(t, -CH3), 1.33(-CH3), 1.33-1.63(m, -CH2-), 1.89(q, - Ph-CH2-), 4.49(t, -0-CH2-), 8.17(m, Ph), 8.30(d, tolyl-3,5-protons), 8.45(d, tolyl-2,6-protons), 8.82(s, B-pyrrole-H). Integration of sig- nal at 1.89 and 4.49 were of equal intensity. b. The crude porphyrins were washed with methanol and then dichloromethane. Both solvents dissolved some material. The uv- visible spectrum of the dichloromethane solution had maxima at 421, 518, 551, 593, and 648 nm. For the methanol solution added to isopropanol, maxima were at 417, 514, 554, 590, and 650 nm. The remaining solid was dissolved into aqueous KOH and its maxima are at 416, 529, 568, 595 sh and 655 nm. The methanol and dichloromethane solutions were combined and the solvents were removed” 5 mL of 30% H202 and 20 mL of acetic acid were added to the porphyrins. The mixture was refluxed for 5 h and porphyrins were decomposed over this time interval. The resulting solution was then tested for aluminum ions. An aqueous solution of ammonium aurin tricarboxylate (aluminon) was added to a portion of the above solution. A small amount of a red precipitate formed which indicated the presence of aluminum ions. E. Friedel-Crafts Acylation of 2% Divinylbenzene-Polystyrene Copolymer Beads with TPP(COCl)uH2. Reaction conditions, such as the temperature and solvent, were varied. The reaction was run at room temperatue and at 50°C and in 114 1,1,2,2-tetrachloroethane or nitromethane. When nitromethane was used, only pale tan beads were obtained, whereas red-brown beads were obtained when 1,1,2,2-tetrachloroethane was used as the solvent. Below is given the procedure which resulted in the highest loading. TPP(COZH)4H2 (150 mg) was treated with 10 mL of thionyl chloride and the resulting solution was refluxed overnight. The excess thionyl chloride was removed at reduced pressure. Next 2% divinylbenzene- polystyrene copolymer beads (1.00 g) were added to the porphyrin tetracid chloride. 1,1,2,2-Tetrachloroethane (10 mL) was added after AlCl3 (150 mg) had been added. The mixture was stirred for 24 h. The beads were collected by filtration and washed with more 1,1,2,2- tetrachloroethane. The beads were then washed with 1 N NaOH, 1 N HCl, water, methanol, and hot DMF. IR, C0 = 1655-1675 cm-1. A 0.10 g sample of the partially pulverized beads was treated with 0.10 g of Cu(OAc)2' -H20 in 20 mL of DMF and heated to 120°C for 3 h. The resulting polymer is red and completely ground to a powder. The copper content was determined from neutron activation analysis. The copper content was 0.83% Cu and in addition, the polymer contained 0.195% A1. Designated as 2% P1-C0-porCu. F. Friedel-Crafts Acylation of 20% Divinylbenzene-Polystyrene Copolymer Beads with TPP(COCl)uH2. Reaction conditions were varied as before. Iki addition, the reaction was also carried out at 100°C. The optimum conditions were found at 50°C in nitromethane. Below is the procedure which gave the best results. IR, (C0) 1655-1675 cm-1. 115 TPP(COZH),4H2 (150 mg) was treated with thionyl chloride as before. The excess was again removed at reduced pressure. One g of 20% divinylbenzene-polystyrene copolymer beads was added to the residue. AlCl3 (150 mg) was added and then nitromethane (10 mL) was added. The resulting mixture was stirred at 50°C for 24 h. The beads were collected by filtration and washed with nitromethane, 1 N NaOH, 1 N HCl, water, methanol, and hot DMF. The beads (0.20 g) were mixed together with 0.20 g of Cu(OAc)2 H20 in 20 mL of DMF. The mixture was then heated at 120°C for 3 h before the beads were collected by filtration. The beads were washed with 0.1 N HCl, water, and methanol. The beads were then soxhlet extracted with methanol for 24 h. The copper complex provided a well resolved ESR spectrum. Neutron activation analysis showed the presence of 0.068% copper and 0.026% aluminum. The sample was designated as P1-CO-porCu. 1. Preparation of P1-C0-porCo. To 0.20 g of the above polymer-bound porphyrin, P1-CO-porH2, was added 0.20 g of CoCl2 6H20 and 20 mL of DMF. The mixture was heated at 120°C for 3 h. After collection by filtration, the beads were washed with 0.1 N HCl, water, and methanol. The sample was soxhlet extracted with methanol for 24 h. Neutron activation analysis showed that 0.085% of cobalt was present. In addition, 0.035% of aluminum was also present. Elemental analysis indicated a cobalt content of 0.05% and a nitrogen content of 0.42%. The nitrogen to cobalt ratio was 35.3 to 1 and the nitrogen to total metal was 10.7 to 1. 116 2. Preparation of P -C0-porCo(B) and P -C0-porFeCl(B). 1 1 A second batch of P1-CO-porH metallated with CoC12°6H20 and FeCl 2 was prepared and it was 2 . Neutron activation analysis showed that only 0.015% of cobalt was present and the aluminum content was below the reliable detection levels. They were designated P1-C0- porCo(B) and P -CO-porFeCl(B). 1 3. Preparation of P -CO-porCu(c) from TPP(COCl)uCu. 1 TPP(COZH)uCu (0.160 g) was treated with 10 mL of thionyl chloride and 4 mL of pyridine. The resulting solution was refluxed overnight. The combined solvents were removed at reduced pressure. To the residue was then added 1.00 g of 20% divinylbenzene-polystyrene copolymer beads, 0.150 g of AlCl and 10 mL of nitromethane. The 3: reaction was heated at 50°C for 18 h and the beads were collected by filtration and were washed as before. The beads were then extracted with methanol for 3 d and with dichloromethane for 2 d. No ESR signal for copper was detected in the sample. The sample was treated with 0.2 g of Cu(OAc)2-H20 in hot DMF as before. After washing, there was no ESR signal. The visible spectrum of the filtrate from the reaction had an absorption at 440 nm but no Soret band. Neutron activation analysis of this sample showed that the copper content was 0.000% and that of aluminum was 0.009%. (L Friedel-Crafts Alkylation of 20% Divinylbenzene-Polystyrene Copolymer Beads. 1. Preparation of P1-CH2-porH2. TPP(CO2hexyl)uH2 (200 mg) was reduced with 180 mg of LAH as before. The resulting hydroxymethylporphyrin was then treated with 20 117 mL of thionyl chloride for 24 h at reflux. The excess thionyl chloride was removed at reduced pressure. The porphyrin was taken up in 30 mL of 1,1,2,2-tetrachloroethane and added to 1.00 g of 20% divinylbenzene- polystyrene copolymer beads and 150 mg of AlCl The reaction was 3. heated at 100°C for 2 CL The beads were collected by filtration and washed with dichloromethane and then methanol. The beads are dark green. 2. Preparation of P1-CH2-porCo. P -CH -porH (0.50 g) and CoC12'6H20 (0.50 g) were mixed 1 2 2 together in 20 mL of DMF and the mixture was heated at 120°C for 3 h. The beads were collected by filtration and were washed as before. Neutron activation analysis showed that the cobalt content was 0.017% and the aluminum content was below the level of detection. Elemental analysis showed that the cobalt content was 0.02% and the nitrogen content was 0.18%. The nitrogen to cobalt ratio was 37.9 to 1. 3. Preparation of P1-CH2-porCu. P -CH -porH (0.50 g) and Cu(OAc)2'H20 (0.50 g) were mixed 1 2 2 together in 20 mL of DMF and the mixture was heated at 120°C for 3 h. The beads were collected by filtration and were washed as before. The ESR spectrum was well resolved for the copper complex. Neutron activa- tion analysis showed that the c0pper content was 0.018% and that of the aluminum was 0.010%. 4. Attempted Preparation of P1-CH2-porH2(B) with TPP(CHZOH)4H2. TPP(CHZOHMH2 (0.100 g) and 20% divinylbenzene-polystyrene copolymer beads (1.00 g) were added to a saturated solution of BF in 3 118 dichloromethane (10 mL). The porphyrin was not soluble in this solution so 10 mL of nitromethane was added. The green solution was refluxed for 7 d while under nitrogen. The beads were washed with pyridine and tetrahydrofuran to yield a nearly colorless sample. The beads (0,20 3) were then treated with 0.20 g of Cu(OAc)2'H20 in 20 mL of DMF at 120°C for 3 h. The beads were collected and washed as before. No copper ESR signal was detected. 5. Preparation of P1-CH2-porCu(B) from TPP(CHZOH)uCu. A 0.50 g sample of 20% divinylbenzene-polystyrene copolymer beads, 100 mg of TPP(CHZOH)uCu, and 150 mg of AlCl were mixed together 3 in 10 mL of 1,1,2,2,-tetrachloroethane. The mixture was stirred at 100°C for 2 d. The beads were collected by filtration and washed with 1,1,2,2-tetrachloroethane. The beads were then soxhlet extracted with THF for 24 h. The ESR spectrum is typical of a dilute copper porphyrin. Neutron activation analysis showed that the copper content was 0.030% and the aluminum content was 0.078%. The IR spectrum showed a weak absorption at 1650 cm-1 which is characteristic of divinylbenzene- polystyrene copolymer adducts of A1013. 6. Preparation of P1-C -0-porH 5 2' A 1.00 g sample of 20% divinylbenzene-polystyrene copolymer beads, 150 mg of T3P(OCSBr)H2, and 150 mg of AlCl were mixed together 3 in 20 mL of 1,1,2,2-tetrachloroethane. The reaction was carried out at 120°C for 2 weeks. The beads were collected by filtration and washed with 1,1,2,2-tetrachloroethane, dichloromethane, and methanol. After air drying, the beads are a light tan. 119 7. Preparation of P1-05-O—porCo. A 1.00 g sample of P1-C -0-porH and 0.50 g of CoC12o6H20 were 5 2 mixed together in 20 mL of DMF and the resulting mixture was heated at 120°C for 3 h. The beads were collected by filtration and washed with 0.1 N HCl, water, and methanol. The beads were then soxhlet extracted with methanol for 24 h. From results for SEM analysis, the cobalt content is 0.006%. H. Preparation of Polymer-Bound Porphyrins with Aminated, 20% Divinylbenzene-Polystyrene COpolymer Beads. 1. Preparation of P -NH-CO-porH 2 2 a. A 50 mg sample of TPP(C02hexyl)qu and 50 mg of aminated, 20% divinylbenzene-polystyrene copolymer beads were mixed in 20 mL of toluene and the mixture was refluxed for 2 d. The beads were collected by filtration and washed with dichloromethane. The beads were still an off white. No reaction had occurred. b. A 240 mg sample of TPP(COZH),‘H2 was treated with 10 mL of thionyl chloride at reflux for 2 h and then at room temperature for another 3 in The excess thionyl chloride was removed at reduced pressure and the porphyrin was kept in a vacuum for 4 h so as to remove the last traces of thionyl chloride. TPP(COCl)uH2 was then mixed with 1.00 g of aminated, 20% divinylbenzene-polystyrene copolymer beads.20 Dichloromethane (20 mL) and triethylamine (1 mL) were then added. The resulting mixture was stirred at ambient temperatures for 24 h before the beads were collected by filtration. The beads were washed with dichloromethane and then treated with 5 mL of triethylamine and 100 mL of methanol at reflux for 0.5 h. The beads were collected and washed 120 with methanol. The beads were dried (25°C and 0.1 mm) for 1 h and then extracted with dichloromethane overnight. The resulting beads are a dark red-brown. 2. Preparation of P -NH-C0-porCu. 2 A 0.50 g sample of P -NH-C0-porH and 0.50 g of Cu(OAc)2°H20 2 2 were mixed togehter in 20 mL of DMF and heated at 120°C for 3 h. The beads were collected by filtration and washed with 0.1 N HCl, water, and methanol. The beads were then soxhlet extracted with methanol for 24 h. Neutron activation analysis showed that the copper content was 0.153%. 3. Preparation of P -NH-CO-porCo. 2 A 0.50 g sample of P -NH-CO-porH and 0.50 g of CoC12'6H20 2 2 were mixed together in 20 mL of DMF and heated at 120°C for 3 h. The beads were collected by filtration and washed with 0.1 N HCl, water, and methanol. The beads were then soxhlet extracted with methanol for 24 h. Neutron activation analysis showed that the cobalt content was 0.358%. 4. Prepartion of PZ-NH-CH -porH 2 2' A 200 mg sample of TPP(COZhexyl),4H2 was reduced as before and the reduced product was then treated with 10 mL of thionyl chloride. The resulting solution was refluxed for 2 h and then allowed to sit overnight. The excess thionyl chloride was removed at reduced pressure. One- g of aminated, 20% divinylbenzene-polystyrene copolymer beads, 0.1 g of’NaHC03, and 20 mL of DMF were added to the porphyrin. The reaction was carried out at 1000C for 16 h. The beads were collected by filtration and washed with dichloromethane. The beads were then soxhlet extracted overnight with dichloromethane. A red-brown product was obtained. 121 5. Preparation of PZ-NH-CHZ-porCu. A 0.20 g sample of P2-NH-CH2-porH2 were mixed together in 20 mL of DMF and the resulting mixture was heated and 0.20 g of Cu(OAc)2°H20 at 120°C for 3 kn The beads were collected by filtration and washed with 0.1 N HCl, water, and methanol. The beads were finally soxhlet extracted with methanol for 24 h. The reddish colored beads were analyzed by neutron activation analysis and the copper content was 0.393%. 6. Preparation of P2-NH-CH2-porCo. A 0.10 g sample of P2-NH-CH2-porH2 20 mL of DMF were heated at 120°C for 3 h. The beads were collected by and 0.20 g of CoC12'6H20 in filtration and washed with 0.1 N HCl, water, and methanol. The beads were soxhlet extracted with methanol for 24 h. Neutron activation analysis showed that the cobalt content was 0.430%. I. Preparation of Polymer-Bound Porphyrins with Chloromethylated, 20% Divinylbenzene-Polystyrene Copolymer Beads. 1. Preparation of P -CH2-NH-porH 3 2' A 230 mg sample of T3P(NHAc)H2 was treated with 120 mL of 6 N hydrochloric acid and 100 mL of 1,2-dichloroethane and the resulting two phase mixture was refluxed for 20 h. After cooling, the organic layer was separated from the aqueous layer. The green organic layer was washed with saturated sodium bicarbonate solution until the free base porphyrin color had returned. The organic layer was dried over anhy- drous magnesium sulfate before the 1,2-dichloroethane was removed at reduced pressure. The NMR spectrum indicated that hydrolysis was not complete for an absorption at 2.32 for the methyl of the acetyl group 122 was present. Integration showed that hydrolysis was about 50% complete. The mixture of porphyrins from above was dissolved into 20 mL of DMF and added to 1.0 g of chloromethylated, 20% divinylbenzene—polysty- rene copolymer beads. The reaction was run at 100°C for 24 h and then the beads were collected by filtration. The beads were then soxhlet extracted with dichloromethane for 24 h and then dried. The beads are a green-brown color. 2. Preparation of P -CH -NH-porCu. 3 2 To 0.40 g of P3-CH2-NH-porH2 and 20 mL of DMF. The mixture was heated to 120°C and the heating was was added 0.15 g of Cu(OAc)2eH20 continued for 3 h. The beads were collected by filtration and then washed with 0.1 N HCl, water, and then methanol. The beads were then soxhlet extracted for 24 h with methanol and then air dried. The resulting copper complex has a well resolved ESR spectrum. Neutron activation analysis showed that the copper content was 0.352%. 3. Preparation of P3-CH2-py-porH2. A 1.00 g sample of chloromethylated, 20% divinylbenzene- polystyrene copolymer beads and 0.22 g of T3P(py)H2 were mixed together in 20 mL of DMF and the reaction was run at 100°C for 24 h. The beads were collected and washed with DMF and then dichloromethane. The beads were soxhlet extracted with dichloromethane for 24 h and then air dried. The beads are a green-brown color. 4. Preparation of P -CH -py-porCu. 3 2 To 0.40 g of P3-CH2-py-porH2 was added 0.15 g of Cu(OAc)2'H20 and 20 mL of DMF. The mixture was heated to 120°C and the heating was continued for 3 h. The beads were collected by filtration and then 123 washed with 0.1 N HCl, water, and then methanol. The beads were then soxhlet extracted for 24 h with methanol and then air dried. The reddish beads have a well defined ESR spectrum for its copper complex. Neutron activation analysis showed that the copper content was 0.310%. 5. Preparation of P3-CH2-O-porH2. A 1.00 g sample of chloromethylated, 20% divinylbenzene- polystyrene copolymer beads, 1.00 g of T3P(0H)H2, and 4.00 g of anhy- drous K2C03 were mixed together and then 40 mL of DMF was added. The reaction was run at room temperature for 7 d. The beads were then collected by filtration and washed with more DMF and extracted with dichloromethane for 24 h. The dark red-brown beads were allowed to air dry. 6. Preparation of P -CH -O-porCu. 3 2 A 0.20g sample of P3-CH2-O-porH2 were mixed together and 20 mL of DMF was added. The mixture was heated and 0.30 g of Cu(OAc)2°H20 to 120°C and after 3 h, the beads were collected by filtration. The beads were washed with 0.1 N HCl, water, and methanol. The beads were then soxhlet extracted for 24 h with methanol and then air dried. The dark red beads gave a resolved ESR spectrum for its copper complex. Neutron activation analysis showed that the copper content was 1.363%. 7. Preparation of P -CH -O-porMnCl. 3 2 A 0.20 g sample of P3-CH2-O-porI-I2 and 0.30 of MnClz°4H20 were mixed together in 20 mL of DMF and treated as in the preparation of P - 3 CH2-0-porCu. The resulting beads were extracted as before. The beads are a dark green in color which is typical of Mn(III)porphyrins. Neutron activation analysis showed that. the ‘manganese content was 124 0.861%. 8. Preparation of P3-CH2-O-porVO. A 0.20 g sample of P3-CH2-O-porH2 and 0.30 g of VOSOu were mixed together in 20 mL of'DMF and treated as in the preparation of P3- CH2-O-porCu. The resulting red-brown beads were extracted with methanol as before. The ESR spectrum of these beads show the presence of magnetically dilute vanadyl porphyrins. 9. Preparation of P -CH -0-porFeCl. 3 2 A 0.20 g sample of P3-CH2-O-porH2 and 0.30 g of FeCl2 were mixed together in 20 mL of DMF and treated as in the preparation of P3- CH2-O-porCu. The resulting red-brown beads were extracted with methanol as before. Iron content was 0.83%. 10. Preparation of P3-CH2-O-porCo. A 0.50 g sample of P3-CH2-O-porH2 (a second batch) and 0.30 g of CoC12-6H20 were mixed together in 20 mL of DMF and treated as in the preparation of P3-CH2-0-porCu. The resulting red-brown beads were extracted with methanol as before. The cobalt content was 0.61% and the nitrogen content was 0.72% N. The nitrogen to cobalt ratio was 4.96 to 1 which is close to the expected 4 to 1. 11. Attachment of 4-Hydroxybenzaldehyde to P3. This polymer-bound aldehyde was prepared from 1.00 g of chloromethylated, 20% divinylbenzene-polystyrene copolymer beads, 1.22 g of 4-hydroxybenzaldehyde, and 1.00 g of anhydrous K2C03 in 20 mL of DMF. The mixture was stirred at room temperature for 24 h. The mixture was filtered and the beads were washed with water and then methanol. The beads were extracted with methanol and then dried. Elemental 125 analysis showed that 6.93% 0 was present or 2.17 mmole of ~O-Ph-CHO per gram of beads were present. 12. Preparation of P3-CH2-0-porH2(B) from P3-CH2-O-Ph-CH0. A 0.50 g sample of P3-CH2-O-Ph-CH0, 0.36 g of'para-tolylalde- hyde, and 0.27 g of pyrrole were mixed together in 100 mL of propionic acid and refluxed for 1 h. The solution was filtered hot and the resulting beads were extensively washed with methanol. The beads were then soxhlet extracted with dichloromethane for 24 IL The beads are black. 13. Preparation of P3-CH2-O-porCu(B). A 0.20 g sample of P3-CH2-O-porH2(B) and 0.20 g of Cu(OAc)2°H20 were mixed together in 20 mL of DMF and treated as in the preparation of P3-CH2-O-porCu. The beads were again soxhlet extracted with methanol. The ESR spectrum showed that extensive dipolar interac- tions between neighboring copper porphyrin units were occurring. Neu- tron activation analysis showed that the copper content was 0.238%. J. Elemental Analysis of Porphyrins, Metalloporphyrins, and Poly- mer-Bound Metalloporphyrins. The elemental analyses were performed by Schwarzkopf Microanalyti- cal Laboratory. Neutron activation analyses were performed on polymer- bound metalloporphyrins. The TRIGA reacter at MSU was used for these determinations and the operator was Jim Carrick. Reference samples were made up in solution form and the samples of beads were used as whole beads in these determinations. 126 K. Scanning Electron Microprobe Analysis of Metalloporphyrin- Containing, 20% Divinylbenzene—Polystyrene Copolymer Beads. Scanning electron microprobe analysis, SEM analysis, was performed on an American Research Laboratories EMX-SVI Microprobe. The x-ray intensities were measured from H} lines of cobalt and copper in order to determine the relative amounts of cobalt and of copper in the divinyl- benzene-polystyrene copolymers. The analyses were performed by Viven Schull. The preparation of the beads consisted of slicing the beads in half and mounting the half bead with its flat surface up on a carbon plate with double sided tape. The half beads were then coated with carbon from a carbon arc in a vacuum before analysis. The exposed mid-section of the beads were scanned by a moving electron beam and the resulting x-ray intensities were recorded. The % Co was determined after corrections were made for the background and the intensity for a standard was determined. %Co = (counts for the bead-counts for the background) % counts for standard The results of analysis for the cobalt and copper were also determined as the ratio of intensity at the center to the intensity at the surface. L. Resonance Raman Spectroscopy. The resonance raman spectra were obtained for 55 HM solutions of TTPCu and TTPAlOH in dichloromethane. The sample of P1-CH -porCu(B) 2 was ground to a powder and placed in a 1 mm tube. Its spectrum was obtained with back scattering geometry. The Spectra were obtained with a Spectra Physics 164-11 krypton laser and the Spex 1401 Ramalog 127 spectrometer. The samples were excited with the 413.1 nm line of the laser. The operator was Pat Callahan. M. Preparation of Samples for ESR Spectral Analysis of TTPCu in TTPHZ. Predetermined amounts of TTPCu and TTPH2 were dissolved in di- chloromethane and methanol was slowly added over several days to co- crystallize the two porphyrins. The crystals were collected by filtra- tion and washed extensively with methanol. The crystals were then allowed to air dry for several days. The samples were then placed in tubes and the ESR spectra were obtained at room temperature on a Varian E—4 Spectrophotometer. The samples of TTPCu in TTPH are given in Table 11. The amounts 2 of each are given as well as the % Cu and mole fraction of TTPCu in each of the samples. N. Experimental Setup and Reaction Conditions for the Autoxida- tion of Cyclohexene. The autoxidation of cyclohexene was performed in a constant- pressure, gas manifold equipped with a gas buret, a mercury leveling bulb, a mineral oil bubbler, and a ground joint for the reaction vessel. The reaction vessel was a 50 mL round bottom flask which was equipped with a side arm with a stop cook. The reaction temperature was controlled at 60°C by a thermocouple immersed into an oil bath which was used to heat the reaction vessel. The oil bath was heated by a nichrome immersion coil and the oil bath was stirred by an overhead mechanical stirrer. The contents of the reaction flask were stirred magnetically. 128 Table 11 Amount of TTPCu in TTPH2 Sample Number mg TTPCu mg TTPH2 Mole Fraction %Cu Cu 1 1 100 0.009 0.086 Cu 2 1 25 0.035 0.33 Cu 3 3 30 0.085 0.79 Cu 4 4 20 0.155 1.44 Cu 5 6 20 0.216 2.00 Cu 6 10 20 0.314 2.89 Cu 7 12 15 0.423 3.85 Cu 8 12 10 0.523 4.73 Cu 9 20 5 0.787 6.94 Cu 10 25 1 0.958 8.34 Cu 11 25 0 1.000 8.94 129 When the metalloporphyrins were used, the metalloporphyrin (0.5 mg) was placed into the reaction vessel. Then the system was evacuated and dioxygen was placed into the system. .A‘K)nm.portion of cyclohexene was then injected by a syringe. The volume of dioxygen uptake was then followed for 2 to 4 h. The reaction was either stopped at 2 h or continued for'24 be In the case of the polymer-bound metalloporphyrins, a 0.100 g portion of the beads were used in place of the metalloporphy- rin. All other conditions were the same. The product composition and identity were determined by gas chro- matography. Authentic samples of cyclohexene, cyclohexene oxide, 2- cyclohexenol, and 2-cyclohexenone were used as references to determine retention times on a column of SE-30. The injector temperature was 150°C, the column temperature was 100°C, and the detector temperature was 150°C. The gas chromatograph used was a Varian Aerograph Model 920 Chromatograph with a thermal conductivity detector. The column length was 10 feet long and 0.25 inch in diameter and it contained 10% SE-3O supported on WHP. 0. Experimental Setup and Reaction Conditions for the Autoxida- tion of Aldehydes. The autoxidation of aldehydes was performed in a constant-pres- sure, gas .manifold which was equipped as for the autoxidation of cyclohexene. The reaction temperature was regulated at 30°C by a thermocouple immersed into the nichrome coil-heated oil bath. Stirring was as before. 130 The reaction vessel was charged by the injection of ethyl acetate solution of TPP(COZEt)uCo and the injection of the aldehyde. The amount of aldehyde injected resulted in a 0.50 M solution of the aldehyde in ethyl acetate. Butanal (1.10 mL) and benzaldehyde (1.30 mL) were used with enough of the TPP(COZEt)uCo solution to bring the total volume to 25.0 mL. The molarity of cobalt porphyrin was 0.0872 mM and 0.0865 mM, respectively. The dioxygen uptake was followed with a gas buret. After 0.5, 1.0, and 2.0 h, two mL of the reaction solution was withdrawn and analyzed for hydrogen peroxide and the peracid content. The weighed solution was treated with 150 mL of 5% sulfuric acid and cracked ice.8u The hydrogen peroxide content was determined by titration with a 0.1 N ceric sulfate solution and with ferroin as indicator. The peracid content was determined with 10 mL of a 10% potassium iodide solution. The liberated iodine was titrated with 0.1 N sodium thiosulfate solution with starch as indicator. P. Additional Instruments. In addition to the instruments mentioned already, these spectro- photometers were used. For IR spectra, Perkin-Elmer 457 and Perkin- Elmer 598 were used. For UV—VIS spectra, a Unicam SP 800 was used. APPENDIX A APPENDIX A Other Polymer-Bound Porphyrins and Metalloporphyrins In addition to the work presented in the main body, coproporphyrin 87 I tetramethyl ester was prepared and then reduced 'with .lithium aluminum hydride in THFSZ. The tetraalcohol was then treated with refluxing solution of thionyl chloride in dichloromethane for 12 hours. The resulting porphyrin was then used in an AlCl -catalyzed Friedel- 3 Crafts alkylation of 20% divinylbenzene-polystyrene cOpolymer beads. After 16 hours, the resulting beads were collected by filtration and extensively washed. They were then metallated with CoC12-6H20 in hot DMF. The resulting sample, P1-C3-porCo, was analyzed with scanning electron microprobe analysis. The scan is shown in Figure 36 and an Ic value of 0.00 was calculated. There was 0.013% Co calculated from the SEM data. Aminated, 20% divinylbenzene-polystyrene c0polymer beads were treated with the sulfonyl chloride of 5,10,15,20-tetrakis(4-sulfonato- phenyl)porphyrin88 i1: dichloromethane anxi triethylamine. After 18 hours, green beads were obtained. The beads were metallated with CoC12°6H20 in hot DMF. The resulting sample, P2-NH-SOZ-porCo, was analyzed by SEM analysis and its scan is shown in Figure 37. The sample had an IQ of 0.43 and a cobalt content of 0.076%. 132 Figure 36. SEM scan of Pl-Cj-porCo. Figure 37. SEM scan of Pz-NH-SOZ-porCo. 133 The values of Ic for these samples are supporting evidence for the results obtained for the other samples. For P1-C3-porCo, IQ of 0.00 again shows that the reactive intermediate in this reaction is unable to effectively penetrate the copolymer matrix. For PZ-NH-SOZ-porCo, its value of 0.43 indicates that diffusion is more efficient. In comparison to P2-NH-CO-porCo (I0 = 0.025), P2-NH-SOZ-porCo is more evenly loaded. This again re-enforces the trend of lower reactivity, better penetra- tion for sulfonyl chlorides are more stable than the analogous acid chlorides. APPENDIX B 134 mL 92 . . . . 60 r 50 - 4O - 30 L 20 '- lO - L, I 1 l 15 3O 45 60 Mimics Figure 38. Autoxidation of Benzaldehyde at 30°C under 1 A B (1 J ATM of 02 ) darkened room ) lighted room ) Pl-CO-porFeCl(B). mL 135 200 " 180 - 160 r 140 - 120- 100 ' 80 " 60 - aci- , J L 1 3O 60 90 Minutes Figure 39. Autoxidation of Benzaldehyde at 30°C under 1 ATM of 02 A) TPP(COZEt)uCo 3) P1 -Co-pomo(8). l 120 136 mL 200 180 160 I40 120 100 80 4O 20 I .1 l 30 6O 90 Minutes Figure 40. Autoxidation of Butanal at 30°C under 1 ATM of 02 A) TPP(COZEt)uCo B) Pl-CO-porCo(B) C) Blank. 137 mL 02 '00- l l A . l 80 " o B 60 - - . 4O - 20- - ' 13” 1 L l 30 60 90 Minutes Figure 41. Autoxidation of Cyclohexene at 60°C under 1 ATM 02 A) TTPCo DD B) T-.(C02hexyl)uCo. 138 mL 'cgz l l I I so- A - so. . ' 40- ' 23()"' ’ £3 . " .3: o . . 1 1 Jr 30 60 90 l20 Minutes Figure 42. Autoxidation of Cyclohexene at 60°C under 1 ATM 02 A) PB-CHZ-O-porCo(whole) B) Pg-NH-CO-porCo(whole). 80 60 4O 20 f* I I l A . B . ' . 1 L 1 L 30 60 90 120 Minutes Figure 43. Autoxidation of Cyclohexene at 60°C under 1 ATM O2 2-0-porCo(ground) B) PZ-NH-CO-porCo(ground). A) PB-CH 140 C (3 C) .lei l L_ 3 4 6 Hours Figure 44. Autoxidation of Cyclohexene at 60°C under 1 ATM 02 A) TTPFeCl B) PB-CHZ-O-porFeCl(used) C) P3-CH2-0-porFeCl(new). APPENDIX C 141 Um- L g L ’_L 400 450 500 550 600 650 700 750 nm Figure 45. UV-VIS spectrum of TPP(COZhexyl)uH2. 4* 1 L 400 450 500 550 600 66 Figure 46. UV-VIS spectrum of TPP(COZhexyl)uZo. 142 JUN 450 500 550 650 700 71?“? Figure 47. UV-VIS spectrum of T3P(py)H2. 4LOO Figure 48. UV-VIS spectrum of T3P\py)Cu. ESCDCDA ESESC) nm 143 TMS 00013 J0- JL so 6 LL 2 O ‘2 PPM Figure 49. 1H NMR spectrum of T3P(py)H2. 144 310090055. 50 gauss I——-i Figure 50. ESR spectrum of PB-CHZ-py-porCu. '185 300C? gauss 5O gauss 1——1 Figure 51. ESR spectrum of Cu 1. 146 3000 gauss I 50 gauss 1———1 Figure 52. ESR spectrum of Cu 2. 147 300|0 gauss 5O gauss 1——1 Figure 53. ESR spectrum of Cu 3. 148 3000 gouss l 50 gauss 1————1 Figure 54. ESR spectra of (1) Cu 4 and (2) Cu 5. 149 3000 gauss 50 90035 }————-1 Figure 55. ESR spectra of (3) Cu 6 and (4) Cu 7. 150 50 gouss 5 300090035 | Figure 56. FEB spectra of (5) Cu 8 and (6) Cu 9. 151 50 gauss 1-—-1 3000 gauss I Figure 57. ESR spectra of (7) Cu 10 and (8) Cu 11. 152 100 gauss 1———1 3400 |gouss Figure 58. ESR spectrum of Cu 7. 153 3400 900 55 100 gauss 1————1 Figure 59. ESR spectrum of Cu 8. 154 3400 gauss 100 gauss F—-——-—1 Figure 60. ESR spectrum of Cu 9. 155 3400 gauss l 100 gauss 1——1 Figure 61. ESR spectrum of Cu 10. 156 3400 gauss 100 gauss 1————1 Figure 62. ESR spectrum of Cu 11. REFERENCES 10. 11. 12. 13. 14. 15. REFERENCES R.H Grubbs, Chemtech. 1977, 512. ~~~~ John I. Crowley and Henry Rapoport, Acc. Chem. 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