Intramolecular kinetic isotope effects in alkane hydroxylations catalyzed by manganese and iron porphyrin complexes
Intramolecular kinetic isotope effects in alkane hydroxylations catalyzed by manganese and iron porphyrin complexes
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锰铁配合物催化烷烃羟基化的分子内动力学同位素效应
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
B. Meunier
中科院分区：
文献类型：
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作者：
A. Sorokin;A. Robert;B. Meunier
以1，3-二氘代金刚烷为底物，研究了锰卟啉和铁卟啉催化烷烃羟基化反应的分子内动力学同位素效应。该底物非常适合测定金属卟啉催化的羟基化中的初级同位素效应：叔C-H（D）键的高化学反应性避免了使产物分析复杂化的副反应，并且叔C-H和C-D键具有相同的空间和立体化学环境。用金刚烷-1，3-d2（98atom%D）和meso-四（2，6-二氯苯基）卟啉和meso-四均三甲苯基卟啉的铁锰配合物[M Ⅲ（TDCPP）Cl和M Ⅲ（TMP）Cl，M Ⅲ =Fe或Mn]作催化剂，测定了动力学同位素效应
Intramolecular kinetic isotope effects (KIEs) in alkane hydroxylations catalyzed by manganese and iron porphyrins have been studied with 1,3-dideuterioadamantane as substrate. This substrate is highly suitable for determination of primary isotope effects in metalloporphyrin-catalyzed hydroxylations: the high chemical reactivity of tertiary C-H (D) bonds avoids side reactions which complicate product analyses, and tertiary C-H and C-D bonds have the same steric and stereochemical environment. Kinetic isotope effects have been determined with adamantane-1,3-d 2 (98 atom % D) and iron and manganese complexes of meso-tetrakis(2,6-dichlorophenyl)porphyrin and meso-tetramesitylporphyrin [M III (TDCPP)Cl and M III (TMP)Cl,M III =Fe or Mn] as catalysts