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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
Source PublicationJOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume797Pages:165-170
AbstractDensity 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.
SubtypeArticle
KeywordHydrogenation Catalytic Mechanism Iridium Density Functional Theory Gamma-valerolactone Levulinic Acid
WOS HeadingsScience & Technology ; Physical Sciences
DOI10.1016/j.jorganchem.2015.08.020
WOS Subject ExtendedChemistry
WOS KeywordCARBON-DIOXIDE ; FORMIC-ACID ; MECHANISTIC INSIGHT ; PLATFORM CHEMICALS ; CO2 REDUCTION ; CONVERSION ; IRIDIUM ; DEHYDROGENATION ; DESIGN ; TRANSFORMATION
Indexed BySCI
Language英语
WOS SubjectChemistry, Inorganic & Nuclear ; Chemistry, Organic
WOS IDWOS:000362379100023
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Document Type期刊论文
Identifierhttp://ir.giec.ac.cn/handle/344007/10871
Collection中国科学院广州能源研究所
AffiliationChinese Acad Sci, CAS Key Lab Renewable Energy, Guangzhou Inst Energy Convers, Guangzhou 510640, Guangdong, Peoples R China
Recommended Citation
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.
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