CuII Lewis Acid-Based Proton-Coupled Electron Transfer Mechanism for Cu-Metal-Organic Framework-Catalyzed NO Release from S-Nitrosoglutathione
CuII Lewis Acid-Based Proton-Coupled Electron Transfer Mechanism for Cu-Metal-Organic Framework-Catalyzed NO Release from S-Nitrosoglutathione
复制标题
CuII路易斯酸基质子耦合电子转移机制用于Cu-金属-有机框架催化S-亚硝基谷胱甘肽释放NO
DOI：
10.1021/acscatal.2c00477
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发表时间：
2022
期刊：
影响因子：
12.9
通讯作者：
Finke, R. G.
中科院分区：
文献类型：
--
作者：
Robert R. Tuttle, Reynolds;Finke, R. G.
提供了以前未知的质子耦合电子转移 (PCET) 机制的证据，该机制可在谷胱甘肽 (GSH) 存在的情况下，由金属有机框架 (MOF) H3[(Cu4Cl)3(BTTri)8] (CuBTTri) 催化内源性 S-亚硝基谷胱甘肽 (GSNO) 释放一氧化氮 (NO)。平衡反应化学计量、活性位点表征和实验速率定律被用来系统地反驳相互竞争的机制假设，出乎意料地导致 PCET 作为所提出的基本机制。 PCET 机制与传统提出的用于通过其他铜基催化剂生成 NO 的形式 CuIIto CuIredox 或其他形式 CuIILewis 酸机制形成对比。所提出的 PCET 机制为用于 GSNO 转化为 NO 的改进 Cu-MOF 催化剂的机械引导合成以及 CuBTTri/GSNO/GSH/NO 系统的计算研究奠定了基础，以进一步测试 CuBTTri 的明确结构、假设反应中间体的结构以及由所提出的 PCET 机制产生的具体问题和假设。
Evidence is provided for a previously unknown proton-coupled electron transfer (PCET) mechanism for nitric oxide (NO) release from endogenousS-Nitrosoglutathione (GSNO) catalyzed by the metal–organic framework (MOF) H3[(Cu4Cl)3(BTTri)8] (CuBTTri) in the presence of glutathione (GSH). The balanced reaction stoichiometry, active site characterization, and the experimental rate law are used to systematically disprove competing mechanistic hypotheses, leading unexpectedly to PCET as the proposed basic mechanism. The PCET mechanism contrasts traditionally proposed, either formally CuIIto CuIredox or other formally CuIILewis acid mechanisms for NO generation by other Cu-based catalysts. The proposed PCET mechanism sets the stage for mechanistically guided syntheses of improved Cu-MOF catalysts for GSNO to NO conversion and for computational investigations on the CuBTTri/GSNO/GSH/NO system as further tests of the well-defined structure of CuBTTri, structures of hypothesized reaction intermediates, and specific questions and hypotheses generated by the proposed PCET mechanism.