Interfacial Tandem Catalysis for Ethylene Carbonylation and C–C Coupling to 3-Pentanone on Rh/Ceria

Abstract

Alkene carbonylation holds the promise to provide atomefficient, clean routes for the production of ester, aldehyde, amide, etc., and CO insertion followed by C−C bond coupling is an ideal route for ketone synthesis. However, alkoxycarbonylation and hydroformylation, in which ester and aldehyde are produced via CO insertion followed by C−O and C− H bond formation, respectively, overwhelmingly dominate the alkene carbonylation reactions. Herein, a promising approach to realize the ethylene carbonylation followed by C−C bond formation to produce 3-pentanone was developed by coupling with alcohol dehydrogenation−transfer−hydrogenation (DTH) reactions on a ceria-supported Rh catalyst. The interfacial Lewis acid−base pair site (Rh δ+ −O−Ce 3+ −O v ), which is constituted by Lewis acidic Ce 3+ −O v (oxygen vacancy) and basic interfacial oxygen of Rh δ+ −O−Ce 3+ , dissociatively activates alcohol and its DTH reactions, which promotes the tandem reaction of ethylene carbonylation and C−C coupling to 3-pentanone. This route provides an alternative way to selectively synthesize higher ketones by one-step olefin carbonylation.

In-situ Synthesis of Nitrogen-doped Graphene Layer Encapsulated Palladium Nanoparticles for Highly Selective Hydrogenation of Vanillin

“…关于催化醛类的还原, 已报道了 Ni [9] 、 Cu [10] 、 Co [11] 、 Pt [12] 、Au [13] 、Ru [14] 、Ir [15] 、Ru [16] 和 Pd [17][18][19][20] 众所周知, 载体的性质影响金属的状态、试剂的吸 附性质和传质过程, 合适的载体可以提升加氢反应的活 性. 现已有碳 [21] 、 聚合物 [22] 、 Al 2 O 3 [23] 、 介孔二氧化硅 [24] 、 沸石 [25] 、碳纳米管 [26] 、金属-有机框架材料(MOF) [27] 、 石墨烯 [28][29][30] 等载体应用于负载 Pd 纳米颗粒.…”

A RuCl3 complex catalytic system for hydroesterification of ethylene, carbon monoxide, and ethanol

“…Propionyl species has been shown to play a crucial role in the ethylene hydroesterification and the source of free hydrogen at the propionyl species is key to the reaction. 3,28,29 There are two types of sources of free hydrogen at the propionyl species, one is the addition of strong acid substances as promoters to the catalytic system, and the other is the dissociation of hydrogen from hydroxyl of alcohols. Ruthenium compounds are excellent catalysts for the transfer of hydroxyl hydrogen from alcohols to olefins, 30,31 allowing the source of free hydrogen at the propionyl species to come from the alcohols avoiding the addition of an acid to the system as a promoter.…”

Ethylene Carbonylation to 3-Pentanone with In Situ Hydrogen via a Water–Gas Shift Reaction on Rh/CeO2

“…For example, alcoholysis of the acyl group produces an ester, , while hydrogenation of the acyl group produces an aldehyde, which is known as hydroformylation . Insertion of CO followed by the creation of a C–C bond holds the promise to produce a ketone, , which is another important family of organic compounds and widely used as solvents, polymer precursors, and pharmaceuticals . For instance, 3-pentanone is always used as a solvent in paint and as a precursor to vitamin E, and the current production of 3-pentanone from ethylene follows a two-step process involving ethylene hydroformylation to propanal, followed by propanal ketonization to 3-pentanone under oxidative conditions. , Ethylene hydroformylation always generates 3-pentanone as one of the byproducts, which provides a potential route for the one-step synthesis of 3-pentanone if the main product of ethylene hydroformylation can be tuned toward 3-pentanone instead of propanal (Scheme S1).…”

“…In situ generated hydrogen, which is widely used for selective hydrogenation reactions, , holds the promise to suppress propionyl hydrogenation and boost the ethylation of the propionyl group to 3-pentanone. Coupled with alcohol dehydrogenation–transfer hydrogenation, ethylene carbonylation to 3-pentanone was attained with the production of 1,1-diethoxyethane or acetone as the byproduct. The water–gas shift (WGS) reaction, in which water acts as a clean hydrogen source, is one of the most important processes for on-site hydrogen production.…”

“…The relative intensity ratio of I 592 / I 462 was significantly enhanced after Rh was supported on ceria. This comes from the fact that metal–support interactions between Rh and ceria greatly promote interfacial oxygen vacancy formation via Rh δ+ –O–Ce–Ov–Ce. ,, When ethylene was adsorbed on the Rh/CeO 2 , three IR bands at 2875, 2940, and 2960 cm –1 appeared, which were assigned to the di-σ-bonded ethylene, and this indicates that ethylene mainly adsorbed on the highly dispersed Rh clusters or nanoparticles (Figure S6). Figure b and c show the IR spectra of adsorbed pyridine on Rh/CeO 2 before and after water adsorption, respectively.…”