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首页> 外文期刊>Chemistry: A European journal >Copper(II)-mediated aromatic ortho-hydroxylation: A hybrid DFT and ab initio exploration
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Copper(II)-mediated aromatic ortho-hydroxylation: A hybrid DFT and ab initio exploration

机译：铜（II）介导的芳族邻羟基化：混合DFT和从头开始探索

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摘要

Mechanistic pathways for the aromatic hydroxylation by [Cu-II(L-1)(TMAO)(0)](-) (L-1 = hippuric acid, TMAO = trimethylamine N-oxide), derived from the O-N bond homolysis of its [Cu-II(L-1)(TMAO)(2)] precursor, were explored by using hybrid density functional theory (B3LYP) and highly correlated ab initio methods (QCISD and CCSD). Published experimental studies suggest that the catalytic reaction is triggered by a terminal copper-oxo species, and a detailed study of electronic structures, bonding, and energetics of the corresponding electromers is presented. Two pathways, a stepwise and a concerted reaction, were considered for the hydroxylation process. The results reveal a clear preference for the concerted pathway, in which the terminal oxygen atom directly attacks the carbon atom of the benzene ring, leading to the ortho-selectively hydroxylated product. Solvent effects were probed by using the PCM and CPCM solvation models, and the PCM model was found to perform better in the present case. Excellent agreement between the experimental and computational results was found, in particular also for changes in reactivity with derivatives of L-1.
机译：[Cu-II（L-1）（TMAO）（0）]（-）（L-1 =马尿酸，TMAO =三甲胺N-氧化物）引起的芳香族羟基化的机械途径，由其键的ON均质化得到[Cu-II（L-1）（TMAO）（2）]前体，使用混合密度泛函理论（B3LYP）和高度相关的从头算方法（QCISD和CCSD）进行了探索。已发表的实验研究表明，催化反应是由末端的铜-氧物种触发的，并且对相应的电子体的电子结构，键合和能级进行了详细的研究。羟化过程考虑了两个途径，即逐步反应和协同反应。结果揭示了明显的协同途径，其中末端氧原子直接攻击苯环的碳原子，从而导致邻位选择性羟基化产物。通过使用PCM和CPCM溶剂化模型探究了溶剂效果，发现PCM模型在当前情况下表现更好。实验和计算结果之间发现了极好的一致性，特别是在与L-1衍生物的反应性变化方面也是如此。

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