Investigation on PCET-accompanied Dimerization of 5-hydroxy-1, 4-naphthoquinone in the Process of Electrochemical Reduction by In Situ FT-IR Spectroelectrochemistry and Density Functional Calculation
Investigation on PCET-accompanied Dimerization of 5-hydroxy-1, 4-naphthoquinone in the Process of Electrochemical Reduction by In Situ FT-IR Spectroelectrochemistry and Density Functional Calculation
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原位FT-IR光谱电化学和密度泛函计算研究电化学还原过程中PCET伴随5-羟基-1、4-萘醌的二聚
DOI：
10.1016/j.electacta.2014.03.049
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发表时间：
2014-06
影响因子：
6.6
通讯作者：
Jin, Baokang
中科院分区：
文献类型：
--
作者：
Li, Dan;Cheng, Longjiu;Jin, Baokang
研究了5-羟基-1，4-萘醌（HNQ）和5-羟基-2-甲基-1，4-萘醌（HMeNQ）在乙腈和质子供体混合介质中的电子转移。虽然具有甲基的HMeNQ和不具有甲基的HNQ之间在结构上仅存在小的差异，但HNQ的还原涉及质子耦合电子转移（PCET）过程，而HMeNQ不涉及。CV和快速扫描红外光谱都支持在电化学还原过程中乙腈中存在中间体HNQ自由基点−和二聚体。密度泛函计算结果表明，HNQ在形成二聚体时发生了质子转移（PT），表明HNQ具有PCET伴随的二聚化机理。此外，二聚体还经历两个连续的ET过程形成醌。当质子供体加入HNQ中时，由于分子间氢键作用，二聚化被抑制，同时PCET过程被中断。
Electron transfers (ET) of 5–hydroxy–1, 4–naphthoquinone (HNQ) and 5–hydroxy–2–methyl–1, 4–naphthoquinone (HMeNQ) have been investigated in acetonitrile and proton donors mixed media. Although there is merely a small difference in structure between HMeNQ, having a methyl, and HNQ, not having a methyl, the reduction of HNQ involves proton coupled electron transfers (PCET) process while HMeNQ not. Both CV and rapid–scan IR spectra support the existence of intermediate HNQradical dot−and dimer in acetonitrile during electrochemical reduction. Density functional calculations show that proton transfers (PT) occur when forming dimer, indicating that HNQ has PCET–accompanied dimerization mechanism. Besides, dimer also undergoes two successive ET processes to form quinone. When proton donors are added to HNQ, dimerization is inhibited owing to intermolecular hydrogen–bonding, accompanying by the interruption of PCET process.
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