Catalytic O-O activation chemistry mediated by iron hangman porphyrins with a wide range of proton-donating abilities
Catalytic O-O activation chemistry mediated by iron hangman porphyrins with a wide range of proton-donating abilities
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DOI：
10.1021/ol034581j
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发表时间：
2003-07-10
期刊：
影响因子：
5.2
通讯作者：
Nocera, DG
中科院分区：
文献类型：
--
作者：
Chng, LL;Chang, CJ;Nocera, DG
本文合成了一系列具有不同供质子能力（pK（a）在2 ~ 25之间）的含侧基的悬式卟啉氧杂蒽（HPX）化合物。它们相应的氯铁（III）配合物促进过氧化氢的过氧化氢酶样分解。铁HPX复合物的整体活性和营业额（TON）是最大的酸性氢键悬垂轴承。这些结果表明，仔细控制分子内质子库存可以显着影响O-O键的催化活化。
graphicA library of hanging porphyrin xanthene (HPX) compounds containing pendant groups with various proton-donating abilities (pK(a) ranging from similar to2 to 25) has been synthesized. Their corresponding chloroiron(III) complexes promote the catalase-like disproportionation of hydrogen peroxide. The overall activity and turnover numbers (TONs) are maximal for iron HPX complexes bearing acidic hydrogen-bond pendants. These results establish that careful control of intramolecular proton inventory can dramatically influence the catalytic activation of O-O bonds.