光和热驱动金催化邻炔基酚与芳基重氮盐的反应:两种机制相似性和差异性的理论研究

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中文摘要：实验上发现,邻炔基酚与芳基重氮盐在热催化和光催化条件下反应可生成不同的产物,然而反应机理尚不清晰.本文采用MS-CASPT2和密度泛函理论方法研究了热和光驱动反应的催化机理.结果表明,热催化和光催化反应的初始历程相同,都是在HCO3-协助下由Au(Ⅰ)催化剂和邻炔基酚反应得到乙烯基Au(Ⅰ)中间体.在此过程中,Au(Ⅰ)催化剂与邻炔基酚反应克服14.8 kcal/mol的能垒生成结构扭曲的配合物,此时邻炔基酚的C≡C三键被活化.随后,乙烯基Au(Ⅰ)中间体和芳基重氮盐形成复合物,热催化和光催化反应开始分叉在黑暗条件下,反应克服15.7 kcal/mol的能垒后生成最终的热催化产物,此时芳基重氮盐的末端N原子直接与乙烯基Au(Ⅰ)中间体的C原子成键.在光照条件下,复合物首先弛豫到激发单重态,经9.8×109 s-1的高效系间窜跃过程衰变到T1态.在T1态,克服7.8 kcal/mol的能垒完成脱氮反应,产生与乙烯基Au(Ⅰ)中间体的Au原子具有相互作用的芳基自由基,随后发生系间窜跃过程到达基态.在基态形成最终的光催化产物.本研究为理解Au(Ⅰ)催化剂与芳基重氮盐的热催化和光催化反应提供了重要的机理见解,发现了无辐射跃迁在光催化反应中的关键作用.

外文标题：Light-and Thermal-Driven Gold-Catalyzed Reaction of o-Alkynylphenols with Aryldiazonium Salts:Computational Insights into Mechanistic Similarities and Differences

外文摘要：It was experimentally found that the gold-catalyzed reaction be-tween o-alkynylphenols and aryldia-zonium salts can lead to different products under thermo-and photo-catalytic conditions;however,the mechanism is elusive.Herein we have employed both MS-CASPT2 and DFT approaches to study the catalytic mechanisms of the corresponding light-and thermal-driven reactions.The results show that both the thermo-and photo-catalytic reactions share some same elementary steps from the Au(Ⅰ)catalyst and o-alkynylphenol,both of which generate a vinyl Au(Ⅰ)intermedi-ate with the aid of HCO3-.In these steps,the formation of a structurally distorted complex of the Au(Ⅰ)catalyst and o-alkynylphenol has a free energy barrier of 14.8 kcal/mol in that the C=C triple bond of o-alkynylphenol is seriously activated.Importantly,the thermo-and pho-to-catalytic reactions start to diverge from the complex formed between the generated vinyl Au(Ⅰ)intermediate and the aryldiazonium salt.Under the dark condition,the reaction pro-ceeds to generate the final thermal product after overcoming a free energy barrier of 15.7 kcal/mol,in which the terminal N atom of the aryldiazonium salt is bonded directly to the C atom of the Au(Ⅰ)species.In the photoirradiation condition,the complex is first excit-ed to its electronically excited singlet state,which then decays to the T1 state with an effi-cient intersystem crossing process of 9.8× 109 s-1.In the T1 state,the denitrogen process com-pletes easily after overcoming a free energy barrier of 7.8 kcal/mol resulting into an aryl radi-cal interacting with the Au atom of the vinyl Au(Ⅰ)species,which is followed by another in-tersystem crossing process from T1 to S0.In the S0 state,the final photocatalytic product is formed.The present work provides important mechanistic details on understanding both thermo-and photo-catalytic reactions of Au(Ⅰ)catalysts and aryldiazonium salts,and most importantly,it is found that nonradiative transitions play an essential role in regulating pho-tocatalytic reactions.

外文关键词：

Photoredox catalysisTransition metal complexDensity funtional theoryRe-action mechanismAu(Ⅰ)catalystPhotophysicsAryldiazonium salto-Alkynylphenol

作者：

金蕊、郭昕怡、彭灵雅、刘向洋、方维海、崔刚龙

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作者单位：

北京师范大学化学学院,理论及计算光化学教育部重点实验室,北京 100875

四川师范大学化学与材料科学学院,成都 610068

关键词：

光氧化还原催化过渡金属配合物密度泛函理论反应机理 Au(Ⅰ)催化剂光物理芳基重氮盐邻炔基酚

基金：

国家重点研发计划Distinguished Professorship of Chang Jiang Scholars of Ministry of Education of China中央高校基本科研业务费专项国家自然科学基金国家自然科学基金

项目编号：

2021YFA15007032223300122003043

出版年：

2024

DOI：

10.1063/1674-0068/cjcp2304029

化学物理学报(英文版)

中国物理学会

化学物理学报(英文版)

CSTPCDEI

影响因子：0.162

ISSN：1674-0068

年,卷(期)：2024.37(1)