Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study
文献类型：期刊论文
| 作者 | Gao, Hui; Chen, Jinzhu
|
| 刊名 | journal of organometallic chemistry
 |
| 出版日期 | 2015-11-15 |
| 卷号 | 797页码:165-170 |
| 关键词 | Hydrogenation Catalytic mechanism Iridium Density functional theory gamma-valerolactone Levulinic acid |
| 英文摘要 | density functional theory (dft) calculations were used to study the mechanisms for hydrogenation of biomass-derived levulinic acid (la) to g-valerolactone (gvl) catalyzed by pnp-ligated (pnp = 2,6-bis(diter-butylphosphinomethyl) pyridine) iridium complexes, ((bupnp)-bu-t)irh3, 1. the transformation proceeds dearomatization/rearomatization including four stages: hydride transfer to give la-h- and dihydride iridium specie ((bupnp)-bu-t)irh2+, methylene proton in the pnp ligand transfer to substrate to form gamma-hydroxyvaleric acid (hva), catalyst regeneration via h-2 splitting, cyclization of hva to gvl. compared with the hydrogenation of co2 catalyzed by the same complex, herein the rate-limiting step is the hydride transfer step rather than the methylene proton transfer. the calculations show that the hydride transfer step has a significantly higher barrier (21.1 vs 5.3 kcal mol(-1) for the hydrogenation of co2). besides, the cyclization is very easily achieved due to the low barrier. as an alternative pathway, different from the above dearomatization/rearomatization process, a base abstracts a proton from the dihydrogen ligand to form the trihydride iridium with a free energy barrier of 24.6 kcal mol(-1). our results will help in the understanding of the mechanisms of hydrogenation of la to gvl catalyzed by metal complexes. (c) 2015 elsevier b.v. all rights reserved. |
| WOS标题词 | science & technology ; physical sciences |
| 类目[WOS] | chemistry, inorganic & nuclear ; chemistry, organic |
| 研究领域[WOS] | chemistry |
| 关键词[WOS] | carbon-dioxide ; formic-acid ; mechanistic insight ; platform chemicals ; co2 reduction ; conversion ; iridium ; dehydrogenation ; design ; transformation |
| 收录类别 | SCI |
| 语种 | 英语 |
| WOS记录号 | WOS:000362379100023 |
| 源URL | [http://ir.giec.ac.cn/handle/344007/10871]  |
| 专题 | 中国科学院广州能源研究所 |
| 作者单位 | Chinese Acad Sci, CAS Key Lab Renewable Energy, Guangzhou Inst Energy Convers, Guangzhou 510640, Guangdong, Peoples R China |
| 推荐引用方式 GB/T 7714 | Gao, Hui,Chen, Jinzhu. Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study[J]. journal of organometallic chemistry,2015,797:165-170. |
| APA | Gao, Hui,&Chen, Jinzhu.(2015).Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study.journal of organometallic chemistry,797,165-170. |
| MLA | Gao, Hui,et al."Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study".journal of organometallic chemistry 797(2015):165-170. |
入库方式： OAI收割
来源：广州能源研究所
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