Al(lll)-Porphyrin 착물에의한올레핀산화반응메카니즘연구

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1 Printed in the Republic of Korea Al(lll)-Porphyrin 착물에의한올레핀산화반응메카니즘연구 w Áùz¼ * w w w yw ( ) Kinetic Investigation of Olefin Oxidation by Al(III)-Porphyrin Complexes Man So Han and Hun Gil Na* Department of chemistry, Dae Jin University, Pochon , Korea (Received October 4, 2005). Al(III)-porphyrin w CH2Cl2 y NaClO w v y e w. s v ey» TPP(5,10,15,20-Tetraphenylporphyrin) (p- X)TPP(X=CH3O, CH3, F, Cl), v styrene (p-x)styrene (X=CH3O, CH3, Cl, Br) w. z Michaelis-Menten Km Vmax w. Michaelis-Menten q l s v ey» d wš, q l ey» w v y M-oxo-olefin x w y ù y e w wš w. : Al(III)-porphyrin, Km, Vmax, Michaelis-Menten, v y ABSTRACT. Kinetic studies of olefin oxidation using Al(III)-porphyrin complexes as catalyst are investigated in CH2Cl2, in which NaClO is used as terminal oxidant. Porphyrins are TPP(5,10,15,20-Tetraphenylporphyrin) and (p- X)TPP(X=CH3O, CH3, F, Cl). Olefins are styrene and ( p-x)styrene (X=CH3O, CH3, Cl, Br). The values of Km and Vmax are calculated from the Michaelis-Menten equation. According to the substituents of substrate and catalyst, kinetic parameters will be measured. Investigating the correlation between the Michaelis-Menten rate parameters and the substituent constants, we were able to analyze the influence on the changes of catalytic activity or the rate determining step during the process of the formation and the dissociation of the M-oxo-olefin. Keywords: Al(III)-porphyrin, Km, Vmax, Michaelis-Menten Equation, Olefin Oxidation yw w, s, fm w v y s ù k š s ƒ»yw w». Ziegler TiCl4 AlEt3 w p w w v v, k sww x kyw w v w e ³ w. w Ÿ 1 w ³ e ³ w» w» w w š š w. w» 2 ü, g p, sww k B12, mj w wš 46

2 .» p s v v w w w z œ yw y š. s v sw 3,4 Mn(III), Fe(III), Co(III) 5,6 w y y kƒ +3ƒ +5ƒ (M=O ) y x V w. 7 Meunier v y y sw y k» w y w. w s v 8 Al(III) y-y w y z w v y y k y +3ƒ w. 9 e s v ù. w, s v w v y y w y (M-oxo) x w. yw v w M-oxo-olefin x w. 7,10 M-oxoolefin w š M-oxo-olefin x w w. ù 10 w w ù» (substrate), y ƒ ƒ. v y y» p ù d w M-oxo-olefin x ù w sw y š w. 11 Al(III)-s v w CH2Cl2 y NaClO w v y e w. s v ey» TPP (p-x)tpp(x=ch3o, CH3, F, Cl), v styrene (p-x)styrene (X=CH3O, CH3, Cl, Br) w. z Michaelis- Menten q l s v 12 ey» d wš, q l ey» w v y M-oxo-olefin x w Al(lll)-Porphyrin w v y 47 y ù y e w wš w. w y š»(cyclic voltammetry) Ÿn d (Optical Transfer Thin Layer Electrode) 13 w yy ƒw s v e y w y y dw.»». propionic acid, (p-x)benzaldehyde(x =CH3O, CH3, H, F, Cl), pyrrole, AlCl3, dimethylformamide (DMF) Aldrich Fluka p. w» w styrene (p-x)styrene(x= CH3O, CH3, Cl, Br) Aldrich p w. CS2, CH3OH, CHCl3, CH2Cl2 1 P2O5 š g GC y w l 14 w w š terminal oxidant w» w NaClO w. w w y w UV/vis spectrophotometer Uvikon 923 q nm š, w»œ Ÿ Varian(Unity Plus AM-300x) FT 1 H-NMR spectrometer CDCl3 w š C, H, N Carlo Erba Strumentazione 1106 w. y y Hewlett Packard 6890 Gas Chromatograph(column: 60 m Supelcowax-10 capillary polar column. FID detector) w. w. 5,10,15,20-Tetraphenylporphyrin(TPP), (p-ch3o)tpp, (p-ch3)tpp, (p-f)tpp (p-cl)tpp w porphyrin propionic acid pyrrole benzaldehyde š y k w w. w 15 column chromatography( :Merck Silicagel 7730, 1 :CHCl3+ CH3OH\(7:3), 2 :CHCl3+CH3OH\(9:1), 3 :CHCl3) 3 w. w CS2, AlCl3 š y j ƒw z evaporator, w CHCl3 w. 16,17 sww w» w» w w, ƒ, y e (Drierite #26800), 4Å š column m g w x

3 48 w Áùz¼. w column chromatography( ; Merck Silicagel 7730) w. Al(p-CH 3O)TPPCl 1 H-nmr(ppm/TMS) in CDCl3: δ 8.91(d, 8H) ring protons; 4.10(s 12H, CH3), (d, phenyl o-h); (d, phenyl m-h) Al(p-CH 3)TPPCl 1 H-nmr(ppm/TMS) in CDCl3: δ 8.89(d, 8H) ring protons; 2.71(s 12H, CH3), (d, phenyl o-h); (d, phenyl m-h) AlTPPCl 1 H-nmr(ppm/TMS) in CDCl3: δ 8.84(d, 8H) ring protons; 8.24(m phenyl o-h); 7.74 (m phenyl m-, p-h) Al(p-F)TPPCl 1 H-nmr(ppm/TMS) in CDCl3: δ 8.82(d, 8H) ring protons; (d, phenyl o-h); (d, phenyl m-h) Al(p-Cl)TPPCl 1 H-nmr(ppm/TMS) in CDCl3: δ 8.80(d, 8H) ring protons; (d, phenyl o-h); (d, phenyl m-h). K m, V max d. v y (1). olefin Al(III)-porphyrin + NaClO A B product (1) (1) w y A B ùký y A y l x y y B A v l. A B w yw y. 11 (benzaldehyde, styrene oxide, acetophenone, phenylacetaldehyde) t chromatogram w y w. (1)» w v styrene (p- X)styrene(X=CH3O, CH3, Cl, Br) š, y NaClO(5 mmol). y d» 0.5~2.5 mm š 1~9 µm w w. 50 ml schlenk tube 18 water circulator(jeiotech-620) w 25 C w 30 m o k z 48 hr g. t (Aldrich) Gas chromatogram w y w, ƒ w» w. w column 60 m capillary polar column(supelcowax-10) š,» FID detector w š, column 70 o C-150 C¾ o 5 C/1min o g.» y (conversion yield) (2) w. conversion yield(%) = {([S]i-[S]f)/[S]i} 100 (2) [S]i =»» [S]f = z û» Ÿn d (OTTLE). w TBAP 0.10 M sw CHCl Al(III)(p- CH3O)TPPCl 1.00 µmol ƒw w k z working electrode Pt, reference electrode Ag Ag +, counter electrode Pt w. ƒ +1.5~-1.5 V wš 0.1 V š d w.»» UV/Vis spectrophotometer HP8453 y š» CV-50W(BAS) w d w. š K m, V max v y (1) (p-ch3)styrene y k Table 1. Al(III)- porphyrin y w» w (M) y (NaClO) l y oxo-metal (MO) 7 x š, MO» (S) (MOS)ƒ x. MOS ƒ (P) w MOS sww (3) ùký. k1 k2 MO+S:MOS M+P (3) k-1» (S) w MOƒ sy ¾» V V=k2 [MOS]. MOƒ S w sy MOS» ([MO]t)» Vmax Vmax=k2 [MOS]t ùký. (3) k-1>>k2 k1[mo][s]=k-1[mos]ƒ š [MO] =[MO]t - [MOS] sx k MOS [MOS] (4). [ MO] +[ S] [ MOS] = [ S] K m (4) (4) Km k-1/k1 Km (1)» w ey ùkü

4 Al(lll)-Porphyrin w v y 49 Table 1. Oxidation of ( p-ch3)styrene catalyzed by Al(III)-porphyrin complexs with NaClO Catalyst Al(p-CH3O)TPPCI (p-ch3)tppcl TPPCl (p-f)tppcl (p-cl)tppcl Conversion (%) Product A(%) a B(%) a C(%) a experimental condition: (p-ch3)styrene (1.85 mm) and catalyst (1 µm). benzyldimethyltetradecylammonium chloride(0.1 mmol)dissolved in 4 ml of CH2Cl2. terminal oxidant(5 mmol) at 25 o C for 48 hrs. a: selectivity in % A: benzaldehyde B: (p-ch3)styrene oxide C: phenylacetaldehyde+acetophenone. V=k2[MOS], Vmax=k2[MOS]t (4) w (5)» (V)» (S) = V [ S] V max K m V max (5) (5) V=1/2Vmax Km», [S]1/2Vmax. yw Km» d Fig. 1. The effect of substrate concentration on the initial rate catalyzed by Al(III)-porphyrins( ). Fig. 2. Plot of rate 1 vs [styrene] 1 for oxidation of styrene catalyzed by Al(III)-porphyrins. w» (5) V -1 vs [S] w -1 r»» l Vmax wì. Km j sy j» v w, y w. 11 (Fig. 1, 2.) Porphyrin ey» w K m, V max w w porphyrin 4 phenyl»ƒ ey» w 4σ 19, p-ch3o (-1.08) < p-ch3(-0.68) < H(0) < p-f(0.24) < p-cl(0.92) ƒ ew Vmax ƒwš Km w (Table 2). Km w MOƒ MOS» v w, Km y w. Vmax» porphyriney» wš. porphyrin ey»ƒ ë porphyrin ƒ w š, ƒ w. ƒ w y (MO)» v ew œ MOS x w w. MOS M+P w

5 50 w Áùz¼ Table 2. Michaelis-Menten parameters for substituted styrene oxidation catalyzed by Al(III)-porphyrin complexes Substrate (p-ch3o)- (p-ch3)- Styrene (p-cl)- (p-br)- Catalyst Km Vmax Km Vmax Km Vmax Km Vmax Km Vmax Al(p-CH3O)TPPCl (p-ch3)tppcl TPPCl (p-f)tppcl (p-cl)tppcl experimental condition: substrate( mm) and catalyst(3 µm), treated with NaClO(1.85 mm) dissolved in 4 ml of CH2Cl2 at 25 o C. Table 3. The Dependencies(ρ) of the Km and Vmax on the value of substitutent porphyrin(4σ) against substrate Substrate ρ(km) (p-ch3o)styrene (p-ch3)styrene styrene (p-cl)styrene (p-br)styrene ρ(vmax) ƒ w Vmax j y ƒ w. Table 3 4σ MOS Km Fig. 4. Porphyrin substituents effects on Vmax for oxidation of substituted styrene catalyzed by Al(III)-porphyrins. Fig. 3. Porphyrin substituents effects on Km for oxidation of substituted styrene catalyzed by Al(III)-porphyrins. (k1) w Vmax(k2) (ρ) ƒƒ w. w Fig. 3, 4 Table 3 ρ Km Vmax 4σ w»» l. Al(III)-porphyrin ey» Km Vmax (ρ)» w., Al(III)-porphyrin w (3) MOS (k1) w (k2) w ey» z w. v y MOS w ƒ x w ƒ w Km Vmax w.

6 Al(lll)-Porphyrin w v y 51 Table 4. The Dependencies (ρ) of the Km and Vmax on the value of substituent styrene (σ+) against catalyst ρ (Vmax) Catalyst ρ (Km) Al(p-CH3O)TPPCl (p-ch3)tppcl (p-h)tppcl (p-f)tppcl (p-cl)tppcl Styrene ey» w K m, V max w styrene ey» Km, Vmax Table 2 w. styrene 1 phenyl»ƒ Okamoto-Brown w σ+ p-ch3o (-0.778) < p-ch3(-0.331) < H(0) < p-cl(0.114) < p-br(0.15) ƒw. styrene ey» σ+ ƒ 20 w Vmax w š. Km ƒ w (Table 2)., styreneey»ƒ w ey Km(k1) ƒw š w Vmax(k2) w. w w y w» e w ùkü». (3) y w ƒ Km(k1) Vmax (k2) ey» (ρ) Table 4 ùkþ. Table 4 ƒ styrene y w Km Vmax σ + w»» l. Al(III)-porphyrin styrene ey» Km Vmax (ρ) MOS x (Km(k1)) w (Vmax(k2)) ƒ w ùkû. Ÿn d (OTTLE) s v y-y kƒ w ƒw yy Ÿn d w rp Ÿ dw. 21 F. Montanari Ÿn d w y (M=O V ) sw y kƒ» w rp y w. 22 w Al(III) y-y s v π w ù. y y k +5ƒƒ ù d w. Fig. 5. Thin-layer spectra of the first oxidation product of (a) ( p-ch3o)tpp and (b) Al(III)(p-CH3O)TPPCl in CH2Cl2/0.1 M TBAP.

7 52 w Áùz¼ Al(III)(p-X)TPPCl(X=CH3O, CH3, H, F, Cl) y š» mw y-y d w ƒ w e dw. 21 Al(III)(p-X)TPPCl+e : [Al()(p-X)TPPCl] [Al(III)(p-X)TPPCl] + e : [Al(III)(p-X)TPP] Al(III)(p-X)TPPCl : [Al(III)(p-X)TPPCl] + +e [Al(III)(p-X)TPPCl] + : [Al(III)(p-X)TPP] + +Cl Al(III)(p-CH3O)TPPCl Ÿn d e w y-y k rp Fig. 5 ùkü. Fig. 5(a) w y k s v rp. y ƒ ƒw s v ù rp q û. s v Ÿ (p-ch3o)tpp [(p-ch3o)tpp] (b) Al(III)(p-CH3O)TPPCl w ùƒ y Al(III) y k w š s v ü yƒ ù. [Al(III)(p- CH3O) TPPCl]+. e w. Ÿ 2 Al(III)(p-CH3O)TPPCl [Al(III)(p-CH3O)TPPCl]+. e w ƒ. NaClO y w v y y M=O V M III -O-Cl w. w y y w» w ƒ w x ww yw w w, x. ƒ Al(III)-porphyrin porphyrin ey» styrene ey» z e w Km(k1) Vmax(k2) (ρ) w MOS x ( w ey (k1)) w (» (k2)), Km Vmax w š ƒ. w y x M=O V M III -O-Cl dw w ü w w. x 1. Yamamoto, A. Organotransition Metal Chemistry; Wiley Interscience: New York, U. S. A., 1986; p Vogtle, F.; Weber, E. Host Guest Complex Chemistry Macrocycles; Springer-Verlag: Heidelberg, Germany., 1985; p Barton, D. H. R.; Martell, A. E.; Sawyer, D. T. The Activation of Dioxygen and Homogeneous Catalytic Oxidation; Plenum Press: New York and London, U. S. A., 1993; p Watanabe, Y. J. Bio. Inorg. Chem. Commentary. 2001, 6, Jorgensen, K. A. Chem. Rev. 1989, 89, Meunier, B.; Carvalho, M.; Bortolini, O.; Momenteau, M. Inorg. Chem. 1988, 27, Razenberg, J. A.; Nolte, R. J.; Drenth, W. M. Tetrahedron Lett. 1984, 25, Bortolini, O.; Meunier, B. J. Chem. Soc., Chem. Commun. 1983, Nam, W.; Valentine, S. J. Am. Chem. Soc. 1990, 112, Ostovic, D.; Bruice, T. C. Acc. Chem. Res. 1992, 25, Bressan, M.; Morvillo, A. Inorg. Chem., 1989, 28, Lineweaver, H.; Burk, P. J. Am. Chem. Soc. 1934, 56, Paulson, S.C.; Elliott, C.M. Anal. Chem. 1996, 68, Perrin, D. D.; Armago, W. L. F. In Purification of Laboratory Chemicals; Pergamon Press: Oxford, U.K., 1988; p Kim, J. B.; Leonard,J. J.; Longo, F. R. J. Am. Chem. Soc. 1972, 88, Harriman, B. Y. J. Chem. Soc. Faraday Trans I. 1982, 78, Harriman, B. Y.; Osborne, A. J. Chem. Soc. Faraday Trans. 1983, Shriver, D. F.; Drezdzon, M. A. The Manipulation of Air-sensitive Compounds; A Wiley-Interscience Publication: New York, U.S.A., 1986; p Mcdaniel, D. H.; Brown, H. C. J. Org. Chem. 1958, 23, Jaffe, H. H. Chem. Rev. 1953, 53, Kadish, K. M.; Cocolios, B. B.; Cornillon, J. L.; Tabard, A.; Guilard, R. Inorg. Chem. 1985, 24, Montanari, F.; Casella, L. Metalloporphyrins catalyzed oxidations; Kluwer Academic Publishers: Dordrecht, Netherlands., 1994; p Fuhrhop, J. H.; Kadish, K. M.; Davis, D. G. J. Am. Chem. Soc. 1973, 95, 5140.