基化合物的生物启发的催化活性上的基甲醇的作用:实验和理论研究
Abani Sarkar1, Arnab Mandal2, Amit Adhikary3
1Department of Chemistry, Indian Institute of Technology Bombay, Mumbai, 400076, India.
Chemistry, an Asian journal
|October 11, 2023
概括
两种化合物具有不同的结构和催化活性. 化合物1是甲基醇和酸酶类反应的双核催化剂,而化合物2是没有活性的1D聚合物,通过DFT计算来解释.
科学领域:
- 协调化学 协调化学
- 催化剂是一种催化剂.
- 计算化学计算化学
背景情况:
- 两种新的基于的化合物,[Zn2 L1 (OAc) 3 (MeOH) ] (1) 和[Zn2 L2 (OAc) 3 ]n (2),被合成和描述.
- 连接物修饰 (morpholinoethyl 与 piperazinylethyl 相比) 导致了不同的结构架构.
研究的目的:
- 为了研究两个具有不同连接体的Zn(II) 复合物的结构多样性和催化作用.
- 使用单晶X射线衍射和DFT计算,阐明结构-活性关系.
主要方法:
- 两种Zn (II) 化合物的合成和表征.
- 单晶X射线衍射 (SCXRD) 用于结构的确定.
- 催化活性测定氧化和酸酶类反应.
- 密度函数理论 (DFT) 计算以了解反应性.
主要成果:
- SCXRD揭示了化合物1的双核结构和化合物2的1D螺旋聚合物,这些结构归因于连接体协调差异.
- 化合物1在3,5-di-tert-butyl catechol的氧化中表现出显著的催化活性 (kcat = 34.94 s−1) 和类似酸酶的活性 (kcat = 24.64 s−1).
- 化合物2没有催化活性,DFT计算表明,基质结合因不利的连接物脱离而受到阻碍.
结论:
- 由连接物修饰产生的结构差异显著影响Zn (II) 复合物的催化性能.
- 化合物1的双核结构和可变的甲醇联结体促进基质结合和高催化活性.
- 化合物2的聚合物结构和刚性协调环境阻止了基板的访问,导致不活性.
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