17 4 2005 7 PROGRESS IN CHEMISTRY Vol. 17 No. 4 Jul., 2005 3 ( 100022) ( 510640), : O627 ; O643. 36 : A : 10052281X(2005) 0420678208 Research of Metalloporphyrins as Mimic Enzyme Catalysts Wang Lanzhi She Yuanbin 3 Xu Weiwei Zhang Yanhui ( Institute of Green Chemistry, Beijing University of Technology, Beijing 100022, China) Ji Hongbing (School of Chemical and Energy Engineering, South China University of Technology, Guangzhou 510640, China) Abstract The applications and mechanism of metalloporphyrins in catalytic oxidation are discussed. Quantum calculation method used in molecular design, uncovering relation between structure and catalytic activity of metalloporphyrins is reviewed. Recent works of authorsresearch group are also introduced. The future application of metalloporphyrins in catalysis is prospected. Key words metalloporphyrins ; oxidation reaction ; catalysts ; quantum calculation 18 P2450 ; 20 30 Rothemund [1 ],, 150 24 48h ( TPP),2004,, : 2004 7, : 2004 9 3 e2mail : sheyb @bjut. edu. cn
4 679 Alder [2 ] ( : (1) ), 141 30min ( ) 10 % 30 %, ; (3) ;, 70 (4) 50 %, Lindsey [3 ] C H CH 2 Cl 2 BF 3 2, C H, TPPH 2 ; 30 % 40 %, 1L, :, 10 % 30 %,, ( ) [4 1991 ] DMF AlCl 3 N 2, TPPH 2 30 % [5,6 ] meso 2[ 42( N, N2 ) ] ( TDMAPPH 2 ) 2[ 42( N, N, H2 ) ] (TDMAPPSH 2 ), ( M2 TDMAPPTPS,M = Co,Cu,Zn,Mg,Mn,Ni) [7,8] 11, Alder Lindsey 1991 12 TXPPH 2 25 % 35 % 3 > 13 000 > 90 % ; P2450 P2450 Eills [12 ] Labinger [13 ] P2450 [8 ],, 90 %, Fe Π [9,10 ] ; (2) ( ), ( P2450) (1) Eills [11 ] 1990 [14 1997 ]
680 17, 8, 2 ( ) ( ), FAB2MS UV2visible IR 2003 Tagliatesta [19 ] 2,62 Fe (TDCPP), MnTPPCl CoTPP, (2),,, oπp2no 2 oπp2clπ2hoπp2och 3 oπp2oh Mn 2 + Fe 2 + Co 2 + Cu 2 + Zn 2 +, 2 R C (O) O, (2a) (2b) (2c) [20 26 CO O 2 NO ] [15, ] Traylor [16 ] 4 8 (2,62 ) Murahashi [17 ] 70, 17 000 1 : : NO 2 > Cl > H > OCH 3 > OH :Mn 2 + > Fe 2 + > Co 2 + : [27 ] 2004 [18 ],T( o2cl) PPFe, 2114 % 24 582 3 :
4 681 [38 2003 ] (4a) (4b) [ TPPFe ] 2 O [ TPPMn ] 2 O [28 ] : 70, 878 2 134 :, C H 21, Colleman [39 ] ( endo2cis) (face to face) 5 6, 41 O O, Jack [29 ], [30 8 10 ], Haber [31 ] Maillard [40 ], F - Cl - Br - I - OH - CH 3 COO - [41 (5) : ] F - > CH 3 COO - > Cl - OH - > Br - > I - 31 P2450 (7) 51, : [32 37 ] 2, ; () PhIO ;
682 17, Fig. 1 The hypothetical catalytic cycle for an alkane to an alcohol using an iron porphyrin complex Fe O 2 Fe (1b) ; Fe O 2 Fe Geier [42 ] Fe O (1 PhIO c), Fe O ( RH) 70 %, Fe O 2 : Fe OH(1 d) ; Fe OH Fe O ( Fe ) 2 Fe 2O2Fe (1g) Machado [43 ] ( ) ( ), : 1 (1e) e (1f) Fe O Fe O ; Fe O (Fe ) 2 ( Fe O Fe ) ; Fe P2450 Fe [46 ], Groves [44 ],, PhIO NaClO H 2 O 2, Ellis [45 ] P2450 (1) : P2450 Fe O 2 (1 a) ;Fe O 2 2
4 683 [47 ] Fe ΠFe Fe, Fe Zakharieva [59 ] ( ) [48 52, ] 1999 Gygrgy [53 ] C H, L [60 ], ( TPPF 20 2 PM3 ZINDOΠ1 Lyons Fe ( ) O) 2002, Fujii [54 ] HOMO 21 11 Gaussian03 HyperChem7. 0 [61,62 ] : (1) E HOMO E L2H (HOMO LUMO ), E HOMO E L2H, (2), ( ) E L2H, E L2H Fukui [55 ] (3) ESR (HOMO) (LUMO), ( ) + 2, Zwaans [56 ] ab initio 3 31 Melvin [57 ] AM1 PM3 9 ; LUMO HOMO H f, Yamamoto [58 ]
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