镍(II)位阻3N给体配合物作为槲皮素-2,4-双加氧酶的模型:末端胺取代基对双加氧反应活性的影响

IF 2 4区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR
Devaraj Karthickram, Nattamai Bhuvanesh, Karuppasamy Sundaravel
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引用次数: 0

摘要

四种末端氮系统衍生二乙基三胺配体的单核镍(II)配合物1-4 [L1=N1-(环己基甲基)- n2 -(2-(环己基甲基)氨基)乙基)乙烷-1,2-二胺,L2=N1-苄基- n2 -(2-(苄基氨基)-乙基)乙烷-1,2-二胺,合成了L3=N1-苯乙基- n2 -(2-(苯乙基氨基)乙基)乙烷-1,2-二胺和L4=N1-(萘-1-甲基)- n2 -(2-(萘-1-甲基)氨基)乙基)乙烷-1,2-二胺及其镍(II)-黄酮酸酯加合物1 a - 4 a作为含镍(II)槲皮素-2,4-双加氧酶的仿生模型。配合物1的XRD分析显示镍(II)与NiN3Cl2O发色团周围存在扭曲的八面体配位环境。DMF的Epa值(3 a<为+0.903 V, 1 a<为+0.931 V, 4 a<为+0.941 V, 2 a<为+0.949 V)表明,加合物中Ni(II)中心的Lewis酸度增加,同时由Ni(II)到fla -的π-反键延伸减小,这是受末端n环烷基/芳基取代基性质的影响。暴露于O2后,DMF中的所有加合物在70℃下以合理的速率常数值(1.8-2.3×10−3 s−1)将结合的fla−分解成开环产物。加合物3a加上−CH2间隔物使苯环比2a更悬垂,减少了末端氮的空间拥挤,从而提高了Ni(II)→黄酮酸盐的反向给π和双氧合速率。通过添加自由基清除剂TEMPO,证实了黄酮氧自由基在双氧降解过程中的形成。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Nickel(II) Complexes of Sterically Hindered 3N Donor Ligands as Models for Quercetin-2,4-Dioxygenase: Impact of Terminal Amine Substituent on Dioxygenolysis Reactivity

Nickel(II) Complexes of Sterically Hindered 3N Donor Ligands as Models for Quercetin-2,4-Dioxygenase: Impact of Terminal Amine Substituent on Dioxygenolysis Reactivity

Nickel(II) Complexes of Sterically Hindered 3N Donor Ligands as Models for Quercetin-2,4-Dioxygenase: Impact of Terminal Amine Substituent on Dioxygenolysis Reactivity

Four mononuclear nickel(II) complexes 14 of terminal nitrogens systematically derivatized diethylenetriamine ligands [L1=N1-(cyclohexylmethyl)-N2-(2-((cyclohexyl- methyl)amino)ethyl)ethane-1,2-diamine, L2=N1-benzyl-N2-(2-(benzylamino)- ethyl)ethane-1,2-diamine, L3=N1-phenethyl-N2-(2-(phenethylamino)ethyl)ethane-1,2-diamine and L4=N1-(naphthalen-1-ylmethyl)-N2-(2-((naphthalen-1-ylmethyl)amino)ethyl)ethane-1,2-diamine] and their nickel(II)-flavonolate adducts 1 a4 a have been synthesized as biomimetic models for nickel(II)-containing quercetin-2,4-dioxygenase. XRD analysis of complex 1 reveals a distorted octahedral coordination environment around nickel(II) with NiN3Cl2O chromophore. The Epa values (+0.903 V for 3 a<+0.931 V for 1 a<+0.941 V for 4 a<+0.949 V for 2 a) in DMF attribute the increase in Lewis acidity of Ni(II) centre in the adducts with concomitant decrease in the extend of π-back bonding from Ni(II)-to-fla as influenced by the nature of terminal Ncycloalkyl/aryl substituents. Upon exposure to O2, all the adducts in DMF at 70 °C decompose the bound fla into their ring-opened products at reasonable rate constant values (1.8–2.3×10−3 s−1). The adduct 3 a with an additional −CH2 spacer makes the phenyl ring more dangling than that in 2 a, renders less steric crowding at terminal nitrogen thereby enhance the Ni(II)→flavonolate π-backdonation and rate of dioxygenation. The formation of flavonoxy radical during the dioxygenative degradation pathway is confirmed by adding free-radical scavenger TEMPO.

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来源期刊
European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
4.30
自引率
4.30%
发文量
419
审稿时长
1.3 months
期刊介绍: The European Journal of Inorganic Chemistry (2019 ISI Impact Factor: 2.529) publishes Full Papers, Communications, and Minireviews from the entire spectrum of inorganic, organometallic, bioinorganic, and solid-state chemistry. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. The following journals have been merged to form the two leading journals, European Journal of Inorganic Chemistry and European Journal of Organic Chemistry: Chemische Berichte Bulletin des Sociétés Chimiques Belges Bulletin de la Société Chimique de France Gazzetta Chimica Italiana Recueil des Travaux Chimiques des Pays-Bas Anales de Química Chimika Chronika Revista Portuguesa de Química ACH—Models in Chemistry Polish Journal of Chemistry The European Journal of Inorganic Chemistry continues to keep you up-to-date with important inorganic chemistry research results.
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