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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >CHEMICAL MECHANISM OF DIOXYGEN ACTIVATION BY MANGANESE(III) SCHIFF BASE COMPOUND IN THE PRESENCE OF ALIPHATIC ALDEHYDES
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CHEMICAL MECHANISM OF DIOXYGEN ACTIVATION BY MANGANESE(III) SCHIFF BASE COMPOUND IN THE PRESENCE OF ALIPHATIC ALDEHYDES

机译:脂肪醛存在下锰(III)席夫夫基化合物对二氧化硫的活化机理

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The manganese(III) complexes with tetradentate Schiff base [H-2(L)] derived from salicylaldehyde and 2-amino-1-benzylamine [abbreviated as H-2(salabza)], ethylenedimaine and 2-hydroxybenzophenone [H-2(7-Phe-salen)], ethylenediamine and 2-hydroxyacetophenone [H-2(7-Me-salen)] showed much higher activity for degradation of tetraphenylcyclopentadienone(TCPN) the singlet oxygen ((1) Delta(g)) scavenger, in the presence of cyclohexanecarboxaldehyde than those of the compounds with H-2(salen) and H-2(salphen), which are derived from salicyaldehyde and ethylenediamine, and o-phenylenediamine, respectively. X-ray crystal structural determinations of the former three compounds and electrochemical data of all the compounds have given strong support for the conclusion that the active species for degradation of TCPN is an acylperoxo Mn-III species coordinated by an aliphatic peracid chelate, which should be derived from aliphatic aldehyde and dioxygen, where the geometry of the tetradentate Schiff base around the Mn-III ion is of cis-beta-configuration. Under the same experimental conditions, the corresponding iron(III) compounds exhibited negligible activity towards the activation of the dioxygen molecule. This was explained in terms of the difference in electronic structures between the two metal ions. (C) 1997 Elsevier Science Ltd. [References: 18]
机译:锰(III)与源自水杨醛和2-氨基-1-苄胺[缩写为H-2(salabza)]的四齿席夫碱[H-2(L)],乙二胺和2-羟基二苯甲酮[H-2( 7-Phe-salen),乙二胺和2-羟基苯乙酮[H-2(7-Me-salen)]表现出更高的降解单线态氧((1)Delta(g))清除剂四苯基环戊二烯酮(TCPN)的活性,在环己烷甲醛存在下,与分别衍生自水杨醛和乙二胺和邻苯二胺的具有H-2(salen)和H-2(salphen)的化合物相比。前三种化合物的X射线晶体结构测定和所有化合物的电化学数据为以下结论提供了有力的支持:TCPN降解的活性物质是由脂族过酸螯合物配位的酰基过氧Mn-III物质。衍生自脂族醛和双氧,其中围绕Mn-III离子的四齿席夫碱的几何结构为顺-β-构型。在相同的实验条件下,相应的铁(III)化合物对双氧分子的活化作用可忽略不计。这是根据两种金属离子之间电子结构的差异来解释的。 (C)1997 Elsevier Science Ltd. [参考:18]

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