用于原子抽象的μ-oxo二铜 (II) 复合物的热力学
Ghazanfar Ali1, Peter E VanNatta1, David A Ramirez1
1Department of Chemistry, University of Utah , Salt Lake City, Utah 84112-0850, United States.
Journal of the American Chemical Society
|December 7, 2017
概括
一个铜复合体经历可逆去质子化,形成能够进行质子-电子转移的基本物种. 这项研究揭示了对甲单氧酶相关的铜氧物种的洞察力.
科学领域:
- 生物有机化学
- 有机金属化学
- 酶机制
背景情况:
- 铜依赖甲单氧酶 (MMO) 酶对于氧化甲至关重要.
- 了解铜-氧物种的反应性是阐明MMO机制的关键.
- 单-μ-复合体{[Cu(tmpa) ]2-(μ-OH)}3+ (1) 作为一个模型系统.
研究的目的:
- 为了研究铜-二-复合物的脱质.
- 描述由此产生的铜氧物种及其反应性.
- 在甲单氧酶的背景下评估[Cu2O]2+的热力学可行性.
主要方法:
- 复合物1在低温 (-30°C) 的可逆去质子.
- 无质子物种的光谱和电化学表征 (2).
- 动力学和热力学分析,包括键解离自由能量 (BDFE) 的测量.
- 根据实验数据校准的密度函数理论 (DFT) 计算.
主要成果:
- 复合物1可逆地脱质,形成基本物种{[Cu(tmpa) ]2-(μ-O) }2+ (2),pKa为24.3.
- 第二种能够从TEMPOH进行协同的质子电子转移.
- 种类2是一种较差的原子抽取器,BDFE (OH) 为77.2 kcal/mol.
- DFT计算表明[Cu2O]2+核在依赖铜的甲单氧酶中具有热力学可行性.
结论:
- 与原子抽象相比,特征铜氧物种表现出明显的反应性.
- 这些发现为依赖铜的甲单氧酶的功能提供了关键的机理洞察力.
- 该研究支持在酶性甲氧化中使用[Cu2O]2+物种的热力学可行性.
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