A linear correlation between energy of LMCT band and oxygenation reaction rate of a series of catecholatoiron(III) complexes: initial oxygen binding during intradiol catechol oxygenation
A linear correlation between energy of LMCT band and oxygenation reaction rate of a series of catecholatoiron(III) complexes: initial oxygen binding during intradiol catechol oxygenation
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DOI：
10.1016/j.jinorgbio.2004.12.004
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发表时间：
2005-03-01
影响因子：
3.9
通讯作者：
Funabiki, T
中科院分区：
文献类型：
--
作者：
Hitomi, Y;Yoshida, M;Funabiki, T
用一系列儿茶酚酸配体作为底物，研究了儿茶酚酸铁（III）配合物的氧反应性。本文研究的所有配合物，[Fe-III(TPA)(R-Cat)]BPh4 (1-9) (TPA：三（吡啶-2-甲基）胺；R- cat：取代儿茶酚酸配体，R = 3,5- bu -t(2) (1), 3,6- bu -t(2) (2), 3,5- me -2 (3), 3,6- me -2 (4), 4- bu -t(5), 4- me (6), H (7), 4- cl(8)和3- cl(9))，仅提供儿茶酚酸配体暴露于O-2时的醇内裂解产物。结果表明，根据电化学性能，1-7可分为两类；即，具有二烷基取代（A族）和单或非取代（B族）儿茶酚酸配体的配合物。尽管它们属于同一类别，但这两组与O-2的反应速率常数的对数与儿茶酚酸-铁（III） LMCT能带的能量呈线性相关，尽管2与相关线有很大的负偏差。在此基础上，lmct的1和3-9的能量依赖性反应性以及2的非常低的反应性。讨论了[Fe-III(TPA)(R-Cat)]BPh4与O-2的反应机理。(C) 2004爱思唯尔公司版权所有。
The oxygen reactivity of catecholatoiron(III) complexes has been examined using a series of catecholate ligands as the substrate. All the complexes examined here, [Fe-III(TPA)(R-Cat)]BPh4 (1-9) (TPA: tris(pyridin-2-ylmethyl)amine; R-Cat: substituted catecholate ligand, R = 3,5-Bu-t(2) (1), 3,6-Bu-t(2) (2), 3,5-Me-2 (3), 3,6-Me-2 (4), 4-Bu-t (5), 4-Me (6), H (7), 4-Cl (8) and 3-Cl (9)), exclusively afforded the intradiol cleaving products of the catecholate ligands upon exposure to O-2. It was revealed that 1-7 can be categorized into two classes based on their electrochemical properties; i.e., the complexes having the dialkyl-substituted (group A) and the mono- or non-substituted (group B) catecholate ligands. In spite of their classification, these two groups show a linear correlation between the logarithm of the reaction rate constant with O-2 and the energy of the catecholate-to-iron(III) LMCT band, although 2 shows a large negative deviation from the correlation line. Based on this LMCT-energy dependent reactivity of 1 and 3-9 as well as the very low reactivity of 2. we have discussed on the mechanisms of the reaction of [Fe-III(TPA)(R-Cat)]BPh4 with O-2. (C) 2004 Elsevier Inc. All rights reserved.