Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism

doi:10.1039/c5ee03256c

	Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism
	Lohr, Tracy L.1; Li, Zhi1,4 ; Assary, Rajeev S.2; Curtiss, Larry A.2,3; Marks, Tobin J.1
	2016
发表期刊	ENERGY & ENVIRONMENTAL SCIENCE (IF:32.4[JCR-2023],34.5[5-Year])
ISSN	1754-5692
卷号	9 期号:2 页码:550-564
发表状态	已发表
DOI	10.1039/c5ee03256c
摘要	The scope and mechanism of thermodynamically leveraged ester RC(O)O-R' bond hydrogenolysis by tandem metal triflate + supported Pd catalysts are investigated both experimentally and theoretically by DFT and energy span analysis. This catalytic system has a broad scope, with relative cleavage rates scaling as, tertiary 4 secondary 4 primary ester at 1 bar H-2, yielding alkanes and carboxylic acids with high conversion and selectivity. Benzylic and allylic esters display the highest activity. The rate law is nu = k[M(OTf )(n)](1)[ester](0)[H-2](0) with an H/D kinetic isotope effect = 6.5 +/- 0.5, implying turnover-limiting C-H scission following C-O cleavage, in agreement with theory. Intermediate alkene products are then rapidly hydrogenated. Applying this approach with the very active Hf(OTf)(4) catalyst to bio-derived triglycerides affords near-quantitative yields of C-3 hydrocarbons rather than glycerol. From model substrates, it is found that RC(O)O-R' cleavage rates are very sensitive to steric congestion and metal triflate identity. For triglycerides, primary/external glyceryl CH2-O cleavage predominates over secondary/internal CH-O cleavage, with the latter favored by less acidic or smaller ionic radius metal triflates, raising the diester selectivity to as high as 48% with Ce(OTf)(3).
收录类别	SCI ; EI
语种	英语
资助项目	Office of Science of the U.S. Department of Energy[DE-AC02-05CH11231]
WOS研究方向	Chemistry ; Energy & Fuels ; Engineering ; Environmental Sciences & Ecology
WOS类目	Chemistry, Multidisciplinary ; Energy & Fuels ; Engineering, Chemical ; Environmental Sciences
WOS记录号	WOS:000369744500021
出版者	ROYAL SOC CHEMISTRY
EI入藏号	20160801956533
EI主题词	Catalysts ; Cerium ; Hydrocarbons ; Hydrogenolysis ; Hydrolysis ; Palladium ; Vegetable oils
EI分类号	Precious Metals:547.1 ; Rare Earth Metals:547.2 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Organic Compounds:804.1
WOS关键词	O-BOND-CLEAVAGE ; BIO-HYDROGENATED DIESEL ; CARBON-OXYGEN BOND ; C-O ; BIODIESEL PRODUCTION ; OXIDATIVE ADDITION ; CATALYTIC DEOXYGENATION ; RECYCLABLE CATALYSTS ; GLYCEROL PRODUCTION ; ARYL CARBOXYLATES
原始文献类型	Article
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/2048
专题	物质科学与技术学院_PI研究组_李智组
通讯作者	Marks, Tobin J.
作者单位	1.Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA 2.Argonne Natl Lab, Div Mat Sci, 9700 S Cass Ave, Argonne, IL 60439 USA 3.Argonne Natl Lab, Ctr Nanoscale Mat, 9700 S Cass Ave, Argonne, IL 60439 USA 4.ShanghaiTech Univ, 100 Haike Rd, Shanghai 201210, Peoples R China
推荐引用方式 GB/T 7714	Lohr, Tracy L.,Li, Zhi,Assary, Rajeev S.,et al. Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism[J]. ENERGY & ENVIRONMENTAL SCIENCE,2016,9(2):550-564.
APA	Lohr, Tracy L.,Li, Zhi,Assary, Rajeev S.,Curtiss, Larry A.,&Marks, Tobin J..(2016).Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism.ENERGY & ENVIRONMENTAL SCIENCE,9(2),550-564.
MLA	Lohr, Tracy L.,et al."Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism".ENERGY & ENVIRONMENTAL SCIENCE 9.2(2016):550-564.