铁_铁_双卟啉和DABCO配位构象对环己烷羟化催化性能的影响_英文_

铁_铁_双卟啉和DABCO配位构象对环己烷羟化催化性能的影响_英文_ 分子催化第 13 卷 第 1 期V o l. 13, N o. 1 ()1999 1999 年 2 月 F eb. JOU RN A L O F M OL ECU L A R CA TA L YS IS CH IN A 研究简报 64, 66 Con f orm a t ion Ef f ec t on Hydroxy la t ion of Cyc lohexan e Ca ta lyzed by () () , - , Iron Iron Porphyr in )1 D im er an d D A BCO w ith M o lecu la r O xygen )2REN Q izh i HUA NG J in wan g M E IW en j ie J I L ian gn ian (S ch ool of C h em is t ry a n d C h em ica l E n g in ee rin g ) 510275 Z h on g sh a n U n iv e rs ity G u a n g z h ou ) ) ((, 2, , , Keywords Iro n iro n po rp h y r in d im e rB iden ta te ligandH yd ro xy la t io n 分类号 614. 33O 70′, S in ce th e ea r ly sa g rea t n um b e r o f d im e r ic m e ta llopo rp h y r in s in w h ich tw o iden t i2 ca l o r d iffe ren t m o ie t ie s a re co va len t ly lin k ed th ro u gh o n e o r m o re b r idge s h ave b een syn2 , , th e sizedw h ich can b e u sed a s m o de ls o f im po r tan t b io lo g ica l sy stem ssu ch a s p ho to syn2 , , . th e sisca ta ly sisp ho to co n du c t io nW e syn th e sized a se r ie s o f iro n po rp h y r in d im e r s co va2 ) ( () ——= 2, 5len t ly lin k ed b y a sho r t f lex ib le a lko x y l ch a in O CH 2 nO n w h ich w e re u sed 450, a s a n ew ca ta ly t ic m o de l sy stem o f cy to ch rom e p an d w e fo u n d th a t th e effec t o f th e : len g th o f a lko x y l ch a in o n th e ca ta ly t ic ac t iv ity o f th e d im e r s is ve ry in te re st in ga ll d im e r s , h ave h igh e r ca ta ly t ic ac t iv it ie s th an th e co r re spo n d in g m o nom e r san d th e ir ca ta ly t ic ac t iv2 . it ie s in c rea sed w ith th e in c rea se o f th e len g th o f th e ch a inT h e re su lt s w e re e lu c ida ted b y 1 .th e equ ilib r ium o f op en an d c lo sed co n fo rm a t io n s o f po rp h y r in d im e r s ) ) ((, 2, . 1 F igS t ruc tu re o f iro n iro n po rp h y r in d im e r 207220, 1998209207. : , 29 , .1998R ece ived rev ised R EN Q izh iF em a leyea r s o ldP h D studen t ) 1, T h is w o rk w a s suppo r ted by N a t io na l N a tu ra l Sc ience Fo unda t io n o f C h inaN a tu ra l Sc ience Fo unda t io n o f Guangdo ng .P ro v ince and R e sea rch Fo unda t io n o f S ta te Key L abo ra to ry o f Coo rd ina t io n C h em ist ry o f N an jing U n ive r sity ) 2.T o w hom co r re spo ndence sho u ld be add re ssed In o rde r to p ro ve th a t th e c lo sed co n fo rm a t io n rea lly p layed an im po r tan t ro le in th e , ca ta ly t ic ac t iv it ie s o f th e po rp h y r in d im e r sw e co n du c ted h yd ro x y la t io n o f cyc lo h ex an e ( ) ) ( , 2, ca ta lyzed b y F e F e po rp h y r in d im e r co va len t ly lin k ed b y a f lex ib le b u to x y ch a in (). 1. F igT h e reac t io n s w e re co r r ied o u t in th e p re sen ce o f zin c pow de r an d ace t ic ac id a s ( th e redu c in g agen t s u n de r m ild co n d it io n s. A r ig id b iden ta te ligan d DA BCO 1, 42d iazo b i2 ) 2. 2 . cyc lo 2. o c tan e w a s added a s th e ax ia l ligan dT h e ca ta ly t ic re su lt s a re listed in1.T ab le ) ) ((, 2, 1 T ab le C a ta ly t ic ac t iv it ie s o f F e F e po rp h y r in d im e r and m o nom e r ababC a ta ly st s F eT P PC l F eT P PC l ) ) ) ) ( ( ( ( , 2, , 2, F e F e d im e r F e F e d im e r 34. 31 7. 21 5. 02 14. 23 TO ()3 : : = ƒ TO tu rno ve r num be rcyc lo h exano l and cyc lo h exano nem o lca ta ly st m o l a : in th e ab sence o f DA BCO ; b: in th e p re sence o f DA BCO : 0. 01; 1. 5 ; 0. 80 ; 5 ; R eac t io n co nd it io n sC a ta ly st mm o lZn mm o lCH 3COO H mm o lC yc lo h exane mL DA BCO () ( ) M eCN ?CH C l= 9?1, 30. 0?0. 5 ?, p u re o xygen 101. 3 k P a, 30 m in. 0. 01 mm o l; so lven t 10 mL 22 F rom T ab le 1, it can b e seen th a t in th e ab sen ce o f DA BCO , th e ca ta ly t ic ac t iv ity o f () ) (, 2, , F e F e d im e r is m o re le ss th e sam e a s th e co r re spo n d in g m o nom e r F eT P PC lsin ce , th e po rp h y r in d im e r h a s tw o fe r r ic ac t ive cen te r sth e m ean tu rno ve r n um b e r o f each fe r r ic ( )61 7. 212. ƒac t ive cen te r is 3. In th e p re sen ce o f 1 equ iv. DA BCO , th e TO n um b e r s o f ( ) ) ( , 2, , bo th F eT P PC l an d F e F e d im e r in c rea seth e add it io n o f th e ax ia l ligan d to th e () [ = ] , fe r r ic cen te r p rom o te s th e fo rm a t io n o f a h igh va len t F e V O sp ec ie sw h ich is th e . o x id izin g in te rm ed ia te in th e ca ta ly t ic cyc leT h e m ean TO n um b e r o f fe r r ic ac t ive cen te r () ()7. 11 14. 22ƒ2, 5. 02.o f th e po rp h y r in d im e r is w h ich is h igh e r th an th a t o f F eT P PC l () , 2 It is b e lived th a t th e se re su lt s a re re la ted to th e sp ec ia l c lo sed co n fo rm a t io n o f F e ) ()(, . 2. F e d im e r cau sed b y th e add it io n o f DA BCO F igS in ce th e m o la r ra t io o f DA BCO ) (2, 2. 2 F igT e rna ry DA BCO d im e r ic F e po rp h y r in com p lexa t io n in th e p re sence 1 . , o f equ ivDA BCO O 2 and reduc ing agen t ) ) ((, 2, 1?1, to F e F e d im e r is th e su itab le b iden ta te ligan d DA BCO can b e bo u n d in side ( ) ) ( ( ), 2, 11 . 22ƒ. th e cav ity o f F e F e d im e r an d fo rm s a stab le te rn a ry addu c t s F igB ( ) ) ( , 2, . Bo th th e ac t ive cen te r s o f F e F e d im e r b in d w e ll w ith DA BCOT h e ste r ic h in 2 () [ =d ran ce cau sed b y th e co fac ia l te rn a ry com p lex favo r s th e fo rm a t io n o f reac t ive F e V () ] . 22, O F igC sp ec ie sso h igh e r ca ta ly t ic ac t iv ity is ga in ed b y ea sie r t ran sfe r o f o x ygen to 分子 催 化 66 第 13 卷 cyc lo h ex an e. T h is ste r ic h in d ran ce can a lso in h ib it th e fo rm a t io n o f in ac t ive Λ2O XO 2 . , d im e r sT h e refo rein th e p re sen ce o f DA BCO po rp h y r in d im e r h a s a h igh e r ca ta ly t ic ac2 ) ) ((, 2, . t iv ity w h ich is m o re th an tw ice th a t o f F eT P PC lSuppo sin g th e F e F e d im e r h ad , , 1 . ,an op en co n fo rm a t io n th en sin ce o n ly equ ivDA BCO w a s added to th e d im e r sy stem () ) (, , 2, o n ly o n e fe r r ic ac t ive cen te r in te rac t s w ith DA BCO so th e ac t iv ity o f F e F e d 10. 04, , 2 . im e r w o u ld b e low e r th an tw ice o f th a t o f F eT P PC lu n le ss equ ivDA BCO w a s . added to th e d im e r sy stemT h e re su lt s de sc r ib ed abo ve show th a t c lo sed co n fo rm a t io n h a s ( ) ) ( , 2, g rea t in f lu en ce o n th e ca ta ly t ic ac t iv ity o f F e F e d im e r fo r th e cyc lo h ex an e h y2 , .d ro x y la t io n an d th e b eh av io r can b e re la ted to th e h igh e r f lex ib ility o f d im e r ic po rp h y r in 1 B iden ta te DA BCO bo u n d in side th e cav ity o f po rp h y r in w a s p ro ved b y th e re su lt s o f H 112.NM R an d H H CO SY R efe ren ce s 1 R en Q izh i, H uang J inw ang, J i L iangn ian. T h e E ffec t o f Co nfo rm a t io n o n th e C a ta ly t ic A c t iv ity o f () () , 22, 1997, 50 5: 181. Iro n M e ta lF ree Po rp h y r in D im e r sS ou th A f r ica J C h em () 2 索继栓, 李树本, 王弘立. ƒƒ42单加氧酶模拟体系催化丙烯环氧化反应. 分子催M n T P P C lN aO C lB eP y () 化, 1991, 5 2: 103 () () 铁 , - 铁 , 双卟啉和 配位构象 D A BCO 对环己烷羟化催化性能的影响 任奇志 黄锦汪 梅文杰 计亮年( )中山大学化学与化工学院 广州 510275 摘要 () () 合成和 表 关于同志近三年现实表现材料材料类招标技术评分表图表与交易pdf视力表打印pdf用图表说话 pdf 征了以 1, 42二氧丁基相连的 p ƒp 型铁 , 2铁, 双卟啉配合物, 并作为催 化剂模拟了细胞色素 单加氧酶催化环己烷的羟化反应. 催化结果表明, 以分子氧为450 P 2重氮双环2, 2, 2 辛 ( 4氧源及还原剂存在的情况下,等当量的刚性双齿配体 1, DA BCO ) ( ) ( ) 烷为轴向配体时, 铁 , 2铁 , 双卟啉的催化活性显著高于相应单体 这是由 . F eT P PC l ( ) ( ) 于双齿配体可以与铁 , 2铁 , 双卟啉形成 1?1 三元夹心式配合物, 从而使双卟啉两个 () 铁, 离子都具有催化活性, 证实了闭合式构象有利于双卟啉催化活性的提高. () () 关键词 铁 , 2铁, 双卟啉 双齿配体 羟化反应