Encumbering the intramolecular pi donation by using a bridge: a strategy for designing metal-free compounds to hydrogen activation
文献类型：期刊论文
| 作者 | Wang ZhiXiang; Lu Gang; Li HaiXia; Zhao LiLi |
| 刊名 | Chinese science bulletin
 |
| 出版日期 | 2010 |
| 卷号 | 55期号:3页码:239-245 |
| 关键词 | Metal-free hydrogen activation Metal-free hydrogenation catalysts Pi donation encumbrance Frustrated lewis pair Ab initio calculations |
| ISSN号 | 1001-6538 |
| DOI | 10.1007/s11434-010-0005-x |
| 通讯作者 | Wang zhixiang(zxwang@gucas.ac.cn) |
| 英文摘要 | On the basis of the flp (frustrated lewis pair) principle, a new strategy has been proposed to construct the "frustration" in designing metal-free hydrogen activation compounds, by using fmo (frontier molecular orbital) analyses and quantum mechanics calculations. unlike the known flps which use bulky substituents to prevent them from forming stable lewis acid/base complexes, the new approach encumbers the intramolecular pi donation from the electron donor to the acceptor (e.g. in bh(2)nh(2)) by using a ch(2) bridge (giving bh(2)ch(2)nh(2)). the strategy is simple and effective. its effectiveness is demonstrated by the small hydrogen activation energy (12.0 kcal/mol) of the model molecule (bh(2)ch(2)nh(2)), which is significantly less than the 42.7 kcal/mol of bh(2)nh(2) and also less than the 18.5 kcal/mol of bh(2)ph(2) whose derivative, r(2)pb(c(6)f(5))(2), has been experimentally shown to be able to activate hydrogen. we also exemplified how to use the strategy to design experimentally more realizable molecules. the example shows promises as a hydrogen activation agent. the strategy can be used to design metal-free catalysts for direct hydrogenation. |
| WOS关键词 | FREE CATALYTIC-HYDROGENATION ; FRUSTRATED LEWIS PAIRS ; HETEROLYTIC DIHYDROGEN ACTIVATION ; DENSITY FUNCTIONALS ; H-2 ; REACTIVITY ; BORANE ; IMINES ; MECHANISM ; AMMONIA |
| WOS研究方向 | Science & Technology - Other Topics |
| WOS类目 | Multidisciplinary Sciences |
| 语种 | 英语 |
| WOS记录号 | WOS:000274109000004 |
| 出版者 | SCIENCE PRESS |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2413661 |
| 专题 | 中国科学院大学 |
| 通讯作者 | Wang ZhiXiang |
| 作者单位 | Chinese Acad Sci, Grad Univ, Coll Chem & Chem Engn, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Wang ZhiXiang,Lu Gang,Li HaiXia,et al. Encumbering the intramolecular pi donation by using a bridge: a strategy for designing metal-free compounds to hydrogen activation[J]. Chinese science bulletin,2010,55(3):239-245. |
| APA | Wang ZhiXiang,Lu Gang,Li HaiXia,&Zhao LiLi.(2010).Encumbering the intramolecular pi donation by using a bridge: a strategy for designing metal-free compounds to hydrogen activation.Chinese science bulletin,55(3),239-245. |
| MLA | Wang ZhiXiang,et al."Encumbering the intramolecular pi donation by using a bridge: a strategy for designing metal-free compounds to hydrogen activation".Chinese science bulletin 55.3(2010):239-245. |
入库方式： iSwitch采集
来源：中国科学院大学
浏览0
下载0
收藏0
其他版本
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。