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首页> 外文期刊>Chemistry: A European journal >Theoretical insights into the mechanism of carbon monoxide (CO) release from co-releasing molecules
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Theoretical insights into the mechanism of carbon monoxide (CO) release from co-releasing molecules

机译：从共释放分子释放一氧化碳（CO）机理的理论见解

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摘要

We used density functional theory to investigate the capacity for carbon monoxide (CO) release of five newly synthesized manganese-containing CO-releasing molecules (CO-RMs), namely CORM-368 (1), CORM-401 (2), CORM-371 (3), CORM-409 (4), and CORM-313 (5). The results correctly discriminated good CO releasers (1 and 2) from a compound unable to release CO (5). The predicted Mn-CO bond dissociation energies were well correlated (R ~2≈0.9) with myoglobin (Mb) assay experiments, which quantified the formation of MbCO, and thus the amount of CO released by the CO-RMs. The nature of the Mn-CO bond was characterized by natural bond orbital (NBO) analysis. This allowed us to identify the key donor-acceptor interactions in the CO-RMs, and to evaluate the Mn-CO bond stabilization energies. According to the NBO calculations, the charge transfer is the major source of Mn-CO bond stabilization for this series. On the basis of the nature of the experimental buffers, we then analyzed the nucleophilic attack of putative ligands (L'=HPO _4 ~(2-), H _2PO ~(4 -), H _2O, and Cl ~-) at the metal vacant site through the ligand-exchange reaction energies. The analysis revealed that different L'-exchange reactions were spontaneous in all the CO-RMs. Finally, the calculated second dissociation energies could explain the stoichiometry obtained with the Mb assay experiments. How do CO-releasing molecules release CO? The DFT inspection of manganese-containing carbon-monoxide-releasing molecules (CO-RMs) leads to the discrimination of good CO releasers from bad ones. Natural bond orbital analysis of the Mn-CO bond reveals that the charge transfer is the major source of stabilization (see figure).
机译：我们使用密度泛函理论研究了五个新合成的含锰的CO释放分子（CO-RM）的一氧化碳（CO）释放能力，即CORM-368（1），CORM-401（2），CORM- 371（3），CORM-409（4）和CORM-313（5）。结果正确地将良好的CO释放剂（1和2）与无法释放CO的化合物（5）区分开。预测的Mn-CO键解离能与肌红蛋白（Mb）分析实验相关性很好（R〜2≈0.9），从而定量了MbCO的形成，从而定量了CO-RM释放的CO量。 Mn-CO键的性质通过自然键轨道（NBO）分析来表征。这使我们能够确定CO-RM中关键的供体-受体相互作用，并评估Mn-CO键的稳定能。根据NBO计算，电荷转移是该系列Mn-CO键稳定的主要来源。根据实验缓冲液的性质，我们然后分析了假定配体（L'= HPO _4〜（2-），H _2PO〜（4--），H _2O和Cl〜-）的亲核攻击。金属的空位通过配体交换反应能量来实现。分析表明，在所有CO-RM中，不同的L'交换反应是自发的。最后，计算的第二解离能可以解释通过Mb分析实验获得的化学计量。释放CO的分子如何释放CO？对含锰的一氧化碳释放分子（CO-RM）的DFT检查导致区分出良好的CO释放剂和不良的CO释放剂。 Mn-CO键的自然键轨道分析表明，电荷转移是稳定化的主要来源（见图）。

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