Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study

doi:10.1016/j.jorganchem.2015.08.020

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	Hydrogenation of biomass-derived levulinic acid to gamma-valerolactone catalyzed by PNP-Ir pincer complexes: A computational study
	Gao, Hui; Chen, Jinzhu
	2015-11-15
发表期刊	JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷号	797 页码:165-170
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.
文章类型	Article
关键词	Hydrogenation Catalytic Mechanism Iridium Density Functional Theory Gamma-valerolactone Levulinic Acid
WOS标题词	Science & Technology ; Physical Sciences
DOI	10.1016/j.jorganchem.2015.08.020
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类目	Chemistry, Inorganic & Nuclear ; Chemistry, Organic
WOS记录号	WOS:000362379100023
引用统计	被引频次：13[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	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.