Origins of Selective C(sp(2))-H Activation Using Transition Metal Complexes with N,N-Bidentate Directing Groups: A Combined Theoretical-Experimental Study
文献类型：期刊论文
| 作者 | Tang, Hao1,3; Zhou, Bingwei2; Huang, Xu-Ri3; Wang, Congyang2; Yao, Jiannian1; Chen, Hui1 |
| 刊名 | ACS CATALYSIS
 |
| 出版日期 | 2014-02-01 |
| 卷号 | 4期号:2页码:649-656 |
| 关键词 | c(Sp(2))-h Activation Transition Metal Coordination Free Energy Reaction Barrier Density Firnctional Theory n N-bidentate Directing Group |
| ISSN号 | 2155-5435 |
| DOI | 10.1021/cs401141k |
| 英文摘要 | The strategy using N,N-bidentate directing groups is a promising way to achieve selective C(sp(2))-H activation inaccessible by that of monodentate directing groups. Herein, through theoretical calculations, we present a rationale behind this strategy, which deciphers its key roles in C-H activation promoted by Ni, Pd, Ru, and Cu. The calculations reveal two key points: (a) Between the two coordination sites of the N,N-bidentate directing group, the proximal one influences more the C-H activation barrier Delta G(double dagger), whereas the distal site affects more the free energy change Delta G relevant to the substrate coordination. (b) Enlarging/shrinking the chelation ring can exert different effects on the reactivity, depending on the metal identity and the ring size. Importantly, our computational results are in full agreement with previous experimental findings concerning reactivity. Furthermore, a prediction about the unprecedented reactivity from our theory is confirmed by our experiments, lending more credence to the rationale and insights gained in this study. |
| 语种 | 英语 |
| WOS记录号 | WOS:000331164000035 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/51165]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Huang, Xu-Ri |
| 作者单位 | 1.Chinese Acad Sci, BNLMS, Inst Chem, Key Lab Photochem, Beijing 100190, Peoples R China 2.Chinese Acad Sci, BNLMS, Inst Chem, Key Lab Mol Recognit & Funct, Beijing 100190, Peoples R China 3.Jilin Univ, Inst Theoret Chem, State Key Lab Theoret & Computat Chem, Changchun 130023, Peoples R China |
| 推荐引用方式 GB/T 7714 | Tang, Hao,Zhou, Bingwei,Huang, Xu-Ri,et al. Origins of Selective C(sp(2))-H Activation Using Transition Metal Complexes with N,N-Bidentate Directing Groups: A Combined Theoretical-Experimental Study[J]. ACS CATALYSIS,2014,4(2):649-656. |
| APA | Tang, Hao,Zhou, Bingwei,Huang, Xu-Ri,Wang, Congyang,Yao, Jiannian,&Chen, Hui.(2014).Origins of Selective C(sp(2))-H Activation Using Transition Metal Complexes with N,N-Bidentate Directing Groups: A Combined Theoretical-Experimental Study.ACS CATALYSIS,4(2),649-656. |
| MLA | Tang, Hao,et al."Origins of Selective C(sp(2))-H Activation Using Transition Metal Complexes with N,N-Bidentate Directing Groups: A Combined Theoretical-Experimental Study".ACS CATALYSIS 4.2(2014):649-656. |
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来源：化学研究所
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