中国科学院大连化学物理研究所机构知识库
Advanced  
DICP OpenIR  > 中国科学院大连化学物理研究所  > 期刊论文
题名: Theoretical Investigations on Rh(III)-Catalyzed Cross-Dehydrogenative Aryl-Aryl Coupling via C-H Bond Activation
作者: Zhao, Dan1, 2;  Li, Xiaoxi2, 4;  Han, Keli1, 2;  Li, Xingwei3;  Wang, Yong2
刊名: JOURNAL OF PHYSICAL CHEMISTRY A
发表日期: 2015-03-26
DOI: 10.1021/jp511564b
卷: 119, 期:12, 页:2989-2997
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical ;  Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Chemistry ;  Physics
英文摘要: The reaction mechanism of Rh(III)-catalyzed cross-dehydrogenative aryl-aryl coupling between benzamides and haloarenes was investigated through detailed density functional theoretical (DFT) studies in terms of regioselectivity and deuterium kinetic isotope effects (KIEs). Three possible routes including one PivO(-)-assisted reaction route and two non-PivO(-)-assisted reaction routes have been studied. The calculated results refute the proposed mechanism (without PivO(-)-assisted process) in the experimental paper and demonstrate that the PivO(-)-assisted reaction mechanism is the most favored. Meanwhile, the calculation revealed that the PivO(-) anion plays a crucial role as a proton acceptor in the C-H bond activation, especially when the second C-H activation of haloarenearene proceeds via a S(E)3 mechanism. The S(E)3 mechanism is presented for the Rh(III)-catalyzed aryl-aryl reaction for the first time. Our mechanism is evaluated by the calculations of the para-/meta-regioselectivity and KIEs. And it is found that the second activation process is the rate-determining step of the whole catalytic cycle. All these calculated properties agree well with the experiment and Glorius's proposal that the Rh(III)-catalyzed cross-dehydrogenative C-C coupling reaction proceeds by dual C-H activations. Our theoretical studies suggest that the Rh(III) complex catalyst strongly affects the mechanisms of the second C-H activation step and thus this work might provide insight into the design of new catalytic systems.
关键词[WOS]: CATALYZED DIRECT ARYLATION ;  ELECTROPHILIC SUBSTITUTION ;  ALKYNES ;  MECHANISM ;  IR ;  COUPLING/CYCLIZATION ;  FUNCTIONALIZATION ;  ALKYNYLATION ;  TEMPERATURE ;  COMPLEXES
语种: 英语
WOS记录号: WOS:000351971400025
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/146145
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

Files in This Item:

There are no files associated with this item.


作者单位: 1.Dalian Univ Technol, Sch Chem, Dalian 116024, Peoples R China
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
3.Chinese Acad Sci, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
4.Jilin Univ, Inst Theoret Chem, State Key Lab Theoret & Computat Chem, Changchun 130023, Peoples R China

Recommended Citation:
Zhao, Dan,Li, Xiaoxi,Han, Keli,et al. Theoretical Investigations on Rh(III)-Catalyzed Cross-Dehydrogenative Aryl-Aryl Coupling via C-H Bond Activation[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2015,119(12):2989-2997.
Service
 Recommend this item
 Sava as my favorate item
 Show this item's statistics
 Export Endnote File
Google Scholar
 Similar articles in Google Scholar
 [Zhao, Dan]'s Articles
 [Li, Xiaoxi]'s Articles
 [Han, Keli]'s Articles
CSDL cross search
 Similar articles in CSDL Cross Search
 [Zhao, Dan]‘s Articles
 [Li, Xiaoxi]‘s Articles
 [Han, Keli]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
  Add to CiteULike  Add to Connotea  Add to Del.icio.us  Add to Digg  Add to Reddit 
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace