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终端化物通过区域选择性质子在由[FeFe]-酶启发的二铁复合体中的稳定

Lucile Chatelain¹, Sven T Stripp², Philippe Schollhammer¹

¹UMR CNRS 6521 Chimie, Electrochimie Moléculaires et Chimie Analytique, Univ. Brest, 6 Avenue Victor le Gorgeu, CS93837, Brest-Cedex 3, 29238, France.

Chemistry (Weinheim an der Bergstrasse, Germany)

|February 3, 2025

概括

铁复合物的质子化产生终端和桥梁化物异构体. 酸强度和硬性因素控制异构体比率,随着时间的推移,终端异构体转化为桥梁.

科学领域:

有机金属化学有机金属化学
生物有机化学生物有机化学
催化剂研究研究

背景情况:

[FeFe]-基酶的活性位点辅因子对于生物生产至关重要.
了解相关的合成复合物有助于模仿酶活性.
铁二元复合体中的质子化通路是催化机制的关键.

研究的目的:

为了研究合成[FeFe]-酶模型复合物的质子化.
为了确定酸强度和固体阻碍如何影响化物同位素的形成.
为了研究由此产生的水化物种的稳定性和异构化动力学.

主要方法:

合成和特征的 [Fe2 ((μ-pdt)) ((κ2-dmpe)) 2 ((CO) 2)) 复合体.
使用不同强度的酸的质子化研究 (例如[HPtBu3][BF4],[HNEt3][BF4],[HPPh3][BF4]).
在不同温度下对化物异构体相互转换的动力分析.

主要成果:

质子化产生终端和桥梁化异构体.
较弱的酸有利于终端化物形成;较强的酸有利于桥接化物.
终端异构体以可测量的动力学 (t1/2 = 在RT时21天) 异构化为桥梁异构体.

结论:

在[FeFe]酶模型中,酸强度和固体效应对于指导质子化结果至关重要.
观察到的异构化突出显示了这些有机金属复合体中的动态过程.
这项工作提供了对合成酶活性位点类型的反应性和稳定性的见解.

关键词:

生物灵感是一种生物灵感.桥梁化物桥梁化物终端化物终端化物 [FeFe] - 酶酶的使用

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