Metal-free homolytic hydrogen activation: a quest through density functional theory computations
文献类型：期刊论文
| 作者 | Zhang, Chenggen1; Lv, Xiangying2; Lu, Gang3; Wang, Zhi-Xiang4 |
| 刊名 | New journal of chemistry
 |
| 出版日期 | 2016 |
| 卷号 | 40期号:9页码:8141-8148 |
| ISSN号 | 1144-0546 |
| DOI | 10.1039/c6nj00557h |
| 通讯作者 | Wang, zhi-xiang(zxwang@ucas.ac.cn) |
| 英文摘要 | The electronic structure of s-cis-1,3-butadiene (ch2=ch-ch=ch2) encouraged us to explore a transition metal (tm) free strategy for homolytic h-2 activation by replacing both terminal ch2 groups of ch2=ch-ch=ch2 with x = nh, o, sih2, ph, s, geh2, ash, and se. the study predicts that the six molecules with x = sih2, ph, s, geh2, ash, and se may activate h-2 with barriers lower than 21.7 kcal mol(-1), but the three with x = ch2, nh, and o have barriers higher than 38.9 kcal mol(-1). unlike homolytic h-2 activation by tm complexes, which occurs on an active site with only one reactive center, the present activations are enabled through an active site with two reactive centers. the greatly increased reactivity of these heavier analogs originates from the significantly reduced eofmo-eufmo gaps (eofmo/eufmo represents the occupied/unoccupied frontier molecular orbital that has the correct symmetry to interact with the h-2 sigma*/sigma orbital). interestingly, h-2 activations by experimentally reported derivatives with x = ph, s, and se were predicted to have experimentally accessible barriers and to be exergonic, which is an exciting observation. the electronic structure of 1,3-dipoles is also suitable for designing geminal active sites for homolytic h-2 activation. |
| WOS关键词 | FRUSTRATED LEWIS PAIRS ; CATALYTIC-HYDROGENATION ; DIHYDROGEN ACTIVATION ; TTF DERIVATIVES ; NONCOVALENT INTERACTIONS ; KETONE HYDROGENATION ; HETEROLYTIC CLEAVAGE ; MOLECULAR TWEEZERS ; ROOM-TEMPERATURE ; BOND ACTIVATION |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Multidisciplinary |
| 语种 | 英语 |
| WOS记录号 | WOS:000382820000104 |
| 出版者 | ROYAL SOC CHEMISTRY |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2376281 |
| 专题 | 中国科学院大学 |
| 通讯作者 | Wang, Zhi-Xiang |
| 作者单位 | 1.Langfang Teachers Univ, Dept Chem & Mat Sci, Langfang 065000, Peoples R China 2.Henan Normal Univ, Sch Environm, Key Lab Yellow River & Huai River Water Environm, Henan Key Lab Environm Pollut Control,Minist Educ, Xinxiang 453007, Henan, Peoples R China 3.Chinese Acad Sci, Fujian Inst Res Struct Matter, State Key Lab Struct Chem, Fuzhou 350002, Fujian, Peoples R China 4.Univ Chinese Acad Sci, Sch Chem & Chem Engn, Beijing 100049, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zhang, Chenggen,Lv, Xiangying,Lu, Gang,et al. Metal-free homolytic hydrogen activation: a quest through density functional theory computations[J]. New journal of chemistry,2016,40(9):8141-8148. |
| APA | Zhang, Chenggen,Lv, Xiangying,Lu, Gang,&Wang, Zhi-Xiang.(2016).Metal-free homolytic hydrogen activation: a quest through density functional theory computations.New journal of chemistry,40(9),8141-8148. |
| MLA | Zhang, Chenggen,et al."Metal-free homolytic hydrogen activation: a quest through density functional theory computations".New journal of chemistry 40.9(2016):8141-8148. |
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来源：中国科学院大学
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