Kinetic studies on the reaction of NO with iron(ii) complexes using low temperature stopped-flow techniques.,Dalton Transactions

当前位置： X-MOL 学术 › Dalton Trans. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Kinetic studies on the reaction of NO with iron(ii) complexes using low temperature stopped-flow techniques.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-06-27 , DOI: 10.1039/d0dt01764g
Pascal Specht ₁ , Martin Oßberger , Peter Klüfers , Siegfried Schindler

Affiliation

Low temperature stopped-flow techniques were used to investigate the reaction of three different iron(II) complexes with nitrogen monoxide. The kinetic studies allowed calculation of the activation parameters from the corresponding Eyring plots for all three systems. The reaction of iron(II) chloride with NO leading to the formation of MNIC (mononitrosyl-iron-complex) and DNIC (dinitrosyl-iron-complex) led to activation parameters of ΔH^‡ = 55.4 ± 0.4 kJ mol⁻¹ and ΔS^‡ = 13 ± 2 J K⁻¹ mol⁻¹ for MNIC and ΔH^‡ = 32 ± 6 kJ mol⁻¹ and ΔS^‡ = −193 ± 21 J K⁻¹ mol⁻¹ for DNIC. Formation of MNIC turned out to be much faster in comparison with DNIC. In contrast, activation parameters for the formation of monoculear [Fe(bztpen)(NO)](OTf)₂ (bztpen = N-benzyl-N,N′,N′-tris(2-pyridylmethyl)-ethylenediamine) ΔH^‡ = 17.8 ± 0.8 kJ mol⁻¹ and ΔS^‡ = −181 ± 3 J K⁻¹ mol⁻¹ supported an associative mechanism. Interestingly, [Fe(bztpen)(CH₃CN)](OTf)₂ does not react with dioxygen at all. Furthermore, activation parameters of ΔH^‡ = 37.7 ± 0.7 kJ mol⁻¹ and ΔS^‡ = −66 ± 3 J K⁻¹ mol⁻¹ were obtained for the reaction of NO with the dinuclear iron(II) H-HPTB complex (H-HPTB = N,N,N′,N′-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane), [Fe₂(H-HPTB)(Cl)₃]. The kinetic data allowed postulation of the mechanisms for all of these reactions.

中文翻译：

使用低温停止流技术进行NO与铁（ii）配合物反应的动力学研究。

低温停止流技术用于研究三种不同的铁（Ⅱ）配合物与一氧化氮的反应。动力学研究允许从所有三个系统的相应Eyring图计算活化参数。氯化铁（II）与NO的反应导致形成MNIC（单亚硝酰基铁络合物）和DNIC（二亚硝酰基铁络合物）导致活化参数ΔH ^‡ = 55.4±0.4 kJ mol ^-1和Δ小号^‡ = 13±2 JK ^-1摩尔^-1为MNIC和Δ ħ ^‡对于DNIC，＝ 32±6kJ mol ^-1和ΔS ^‡＝ -193±21JK ^-1 mol ^-1。与DNIC相比，MNIC的形成要快得多。相反，用于形成单核[Fe（bztpen）（NO）]（OTf）_2的激活参数（bztpen = N-苄基-N，N '，N'-三（2-吡啶基甲基）-乙二胺）ΔH ^‡ = 17.8±0.8 kJ mol ^-1和ΔS ^‡ = −181±3 JK ^-1 mol ^-1支持一种关联机制。有趣的是，[Fe（bztpen）（CH ₃ CN）]（OTf）₂根本不与双氧反应。此外，对于NO与双核铁（II）H-HPTB络合物的反应，获得的活化参数为ΔH ^‡ = 37.7±0.7 kJ mol ^-1和ΔS ^‡ = -66±3 JK ^-1 mol ^-1（ H-HPTB = N，N，N '，N'-四（2-苯并咪唑基甲基）-2-羟基-1,3-二氨基丙烷），[Fe ₂（H-HPTB）（Cl）₃]。动力学数据可以推测所有这些反应的机理。

更新日期：2020-07-17

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11