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首页> 外文期刊>Chemistry: A European journal >Isolation of an Oxomanganese(v) Porphyrin Intermaediate in the Reaction of a Manganese(III) Porphyrin Complex and H_2O_2 in Aqueous Solution
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Isolation of an Oxomanganese(v) Porphyrin Intermaediate in the Reaction of a Manganese(III) Porphyrin Complex and H_2O_2 in Aqueous Solution

机译：锰（III）卟啉配合物与H_2O_2水溶液反应中间氧化锰（v）卟啉的分离

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The reaction of [Mn-(TF_4TMAP]](CF_3SO_3)_5 (TF_4TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H_2O_2 (2 equiv) at pH 10.5 and 0 deg C yielded an oxomanganese(v) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-1-phenyl-2-propyl hyroper-oxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H_2~18O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF_4TMAP)]~(5+) with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. whereas the O-O bond of hydroperoides containing an electron-donating tert-alkyl group is cleaved homolytically,a n electron-with-drawing substituent such s an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heteolysis. The mechanism of the O-O bond cleavage of H_2O_2 depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on ~18O incoroporation from H_2~18O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF_4TMAP)]~(5+) and KHSO_5 in buffered H_2~18O solutions. A high proportion of ~18O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.
机译：[Mn-（TF_4TMAP]]（CF_3SO_3）_5（TF_4TMAP = meso-tetrakis（2,3,5,6-tetrafluoro-N，N，N-trimethyl-4-aniliniumyl）porphinato dianion）与H_2O_2（2当量）在pH 10.5和0摄氏度下产生水溶液中的oxomanganese（v）卟啉配合物1，而在叔烷基氢过氧化物（如叔丁基氢过氧化物）和2-从[Mn（TF_4TMAP）]〜（5+）的反应中，甲基-1-苯基-2-丙基过氧化物。配合物1能够环氧化烯烃并与H_2〜18O交换氧，而配合物2不能环氧化烯烃。 ）在pH范围为3-11的各种氧化剂下，发现氢过氧化物的OO键裂解对氢过氧化物取代基和反应溶液的pH值敏感，而含有给电子叔烷基的氢化合物的OO键裂解被间位裂解的吸电子取代基，例如间氯过氧苯甲酸（m-CPBA）的酰基tes O-O键溶血。 H_2O_2的O-O键裂解机理取决于反应溶液的pH值：低pH时O-O键均质化占主导地位，高pH值时O-O键杂质化成为主要途径。通过在缓冲的H_2中用[Mn（TF_4TMAP）]〜（5+）和KHSO_5进行卡马西平（CBZ）的环氧化，研究了pH对H_2〜18O从〜2O〜18O进入氧化产物的影响。 〜18O解决方案。在所有pH值下，高比例的〜18O被掺入CBZ-10,11-氧化物产品中，但是该比例不受反应溶液的pH值的显着影响。

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