Solvent-Assisted Ruthenium Complex Catalyzes Hydrogenation and the Reductive Amination of Carbon Dioxide DOI

Huiying Liao,

Manyu Chen,

Yuan Ma

et al.

Industrial & Engineering Chemistry Research, Journal Year: 2022, Volume and Issue: 61(41), P. 15156 - 15168

Published: Oct. 5, 2022

Catalytic hydrogenations represent fundamental processes in the synthesis of fine chemicals and chemical intermediates, allowing for atom-efficient clean functional group transformations. Herein, we have developed a highly efficient, robust catalytic system consisting ruthenium hydride complex [RuH(CO)(dppp)(en)]Cl tetrabutylammonium acetate (TBAOAc), where former was employed as catalyst selective hydrogenation methyl levulinate (ML) to γ-valerolactone (GVL) with molecular hydrogen under mild reaction conditions without any base additives, while latter used low-temperature molten salt solvent assisting reaction. After reaction, solid TBAOAc can settle down spontaneously due immiscibility weak polar extraction solvent, leading separation products from mixture. Furthermore, leaching-resistant maintains its activity consecutive recycles. Notably, not only acted media but also played an important role improving performance via coordination OAc– Ru sites. In contrast poor ML catalyzed by conventional organic solvents, superior achieved using media. NMR, HR-ESI-MS analysis, deuterium-labeling studies indicated that ligand exchange could happen between formation Ru–OAc species, which promote H2 activation, dissociation sequential hydrogenation. Finally, this has been extended smoothly N-formylation large variety amines carbon dioxide showed high activity, stability, selectivity toward formamides. This study identifies reason TBAOAc-assisted catalyzing provides new insights optimize sustainability procedure conversion biomass-derived platform molecules CO2.

Language: Английский

Recent advances in the catalytic production of bio-based diol 2,5-bis(hydroxymethyl)furan DOI Creative Commons
Wenguang Zhao, Feng Wang,

Kangyu Zhao

et al.

Carbon Resources Conversion, Journal Year: 2023, Volume and Issue: 6(2), P. 116 - 131

Published: Jan. 4, 2023

Biomass-derived 2,5-bis(hydroxymethyl)furan (BHMF) has received great attention and interest due to its broad application prospects in polyesters medicine. Over the past decades, catalytic systems including thermocatalytic, biocatalytic, electrocatalytic, photocatalytic hydrogenation of 5-hydroxymethylfurfural (HMF) into BHMF have been developed a extent. To understand present status challenges production, this review systematically evaluates recent findings developments HMF through various reaction systems, with an emphasis on catalyst screening, synthesis processes, mechanism. Furthermore, few potential research trends are also proposed, order provide innovative ideas for further exploration simpler, efficient, economical way.

Language: Английский

Citations

28
Pd nanoparticles encapsulated in MOF boosts selective hydrogenation of biomass derived compound under mild conditions DOI
Yushan Wu,

Yawen Tong,

Heng Liang

et al.

Chemical Engineering Journal, Journal Year: 2023, Volume and Issue: 460, P. 141779 - 141779

Published: Feb. 7, 2023

Language: Английский

Citations

24
Advances in Catalytic Routes for the Homogeneous Green Conversion of the Bio‐Based Platform 5‐Hydroxymethylfurfural DOI
Alessandro Messori, Andrea Fasolini, Rita Mazzoni

et al.

ChemSusChem, Journal Year: 2022, Volume and Issue: 15(13)

Published: April 6, 2022

5-Hydroxymethylfufural (HMF) is an intriguing platform molecule that can be obtained from biomasses and lead to the production of a wide range products, intermediates, or monomers. The presence different moieties in HMF (hydroxy, aldehyde, furan ring) allows carry out transformations such as selective oxidations hydrogenations, reductive aminations, etherifications, decarbonylations, acetalizations. This great chance biorefinery perspective but requires development active highly catalysts. In this view, homogeneous catalysis efficient conversion at mild reaction conditions. Review discussed recent achievements catalysts application transformations. effects metal nature, ligands, solvents, conditions were reported critically reviewed. Current issues future chances have been presented drive studies toward more scalable processes.

Language: Английский

Citations

30
Ru-Nitrosyl Complex Salts as Efficient Catalysts for the Reversible CO2 Hydrogenation/FA Dehydrogenation in Ionic Liquids DOI Creative Commons
José Tiago Menezes Correia, Valeria Nori, Mike Steffen Bernhard Jørgensen

et al.

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: April 15, 2025

We demonstrate that bench-stable ruthenium-PNP nitrosyl complex salts with different counteranions (Cl-, BF4 -, BPh4 PF6 and OTs-) a ruthenium-POP are competent (pre)-catalysts for the CO2 hydrogenation to formic acid (FA) at low temperatures in ionic liquids. Only minor effect of variation counteranion was observed, weakly basic liquids such as EMIM OAc, BMIM HCO2 were suitable this transformation, affording conversions up 94 mol % compared liquid (FA/IL) turnover numbers (TONs) 1305. Importantly, same catalytic system also efficient dehydrogenation back H2, >95% (949 TON) after 3 h 95 °C. To investigate application protocols hydrogen storage transportation purposes, hydrogenation/dehydrogenation cycles performed, showing new can promote 10 reversible hydrogenation/FA before losing its activity.

Language: Английский

Citations

1
Promising Catalytic Application by Pincer Metal Complexes: Recent Advances in Hydrogenation of Carbon‐Based Molecules DOI
Krishna K. Manar, Jing Cheng, Yang Yang

et al.

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(15)

Published: April 19, 2023

Abstract In the last two decades, pincer metal complexes have been highly utilized as catalysts for a variety of organic transformations in both industrial and social applications. Owing to extraordinary chemical characteristics, such extra thermal stability easy functionalization, they were extensively generating novel catalytic species. Besides, activity these was achieved with high atom economy eco‐friendly routes. Recently, exhibited excellent behaviour towards various immerging systems, hydrogenation CO 2 , nitriles, amides, esters, olefins alkynes, which are valuable production, academic research, green environment. The main goal this reviewwas highlight how function reactions, well their mechanistic studies. Specifically, we focus on most updated advancements few years. Some outlooks future suggestions further related work conclude paper.

Language: Английский

Citations

14
Well-Defined Robust Imidazole-Based Metal–Ligand Cooperative Ru(II)-para-Cymene for Transfer Hydrogenation of Furanic Aldehydes Using Renewable Alcohols DOI
Rahul Daga Patil, Sanjay Pratihar

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(16), P. 6206 - 6219

Published: April 9, 2024

The present study addresses the challenges in catalytic transfer hydrogenation using methanol/ethanol for converting biomass-derived furanic aldehydes to furfuryl alcohols. introduction of air-stable Ru(II)-para-cymene catalysts with imidazole-based metal–ligand cooperativity represents a significant advancement. Spectroscopic, situ monitoring, labeling, and DFT investigations reveal mechanistic details, highlighting role Ru–H generation through dehydrogenation Ru(II)-alkoxide intermediates. Hydride proton transfers are facilitated by interconvertible coordination mode imidazole Ru(II)–para-cymene, which is crucial maintaining catalyst's efficiency selectivity. Notably, pKa N–H coordinated significantly influences reactivity, following specific order depending on attached heterocycle: > pyridine thiazole. This correlates well computed activation barrier generation. catalyst exhibits ease synthesis, stability air moisture, use renewable hydrogen sources, excellent selectivity aldehydes, applicability various potential large-scale processes. These features collectively contribute economic sustainable nature both protocol, providing valuable contribution field hydrogenation.

Language: Английский

Citations

6
Direct biomass valorisation to γ-valerolactone by Ru-PNP catalysed hydrogenation in acid DOI Creative Commons
Sakhitha Koranchalil, Martin Nielsen

EES Catalysis, Journal Year: 2024, Volume and Issue: 2(3), P. 803 - 810

Published: Jan. 1, 2024

Simultaneous homogeneous catalytic hydrogenation and acid-treatment of carbohydrates yields GVL in excellent from substrates raw biomass to monosaccharides.

Language: Английский

Citations

5
Base-Free Synthesis of Furfurylamines from Biomass Furans Using Ru Pincer Complexes DOI Open Access
Danielle L. J. Pinheiro, Martin Nielsen

Catalysts, Journal Year: 2021, Volume and Issue: 11(5), P. 558 - 558

Published: April 28, 2021

We report the first example of employing homogeneous organometal-catalyzed transfer hydrogenation for selective reductive amination furfurals to furfurylamines. An efficient, chemoselective, and base-free method is described using Ru-MACHO-BH as catalyst iPrOH H donor. The tolerates a range substituents affording moderate excellent yields.

Language: Английский

Citations

21
Rational synthesis of ruthenium-based metallo-supramolecular polymers as heterogeneous catalysts for catalytic transfer hydrogenation of carbonyl compounds DOI

Zi-Jie Gong,

Yemineni S. L. V. Narayana, Yen‐Chun Lin

et al.

Applied Catalysis B Environment and Energy, Journal Year: 2022, Volume and Issue: 312, P. 121383 - 121383

Published: April 8, 2022

Language: Английский

Citations

15
Selective hydrogenation of HMF to DHMF with Ru–PNP complexes in ionic liquids DOI Creative Commons
Valeria Nori,

Haliru Abdulrahman Sidi,

Martin Nielsen

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(16), P. 12791 - 12796

Published: Jan. 1, 2025

This study explores hydrogenating HMF to DHMF using Ru–PNP catalysts in ILs, achieving up 99% conversion and yield under mild conditions, with ILs preventing polymerization humins.

Language: Английский

Citations

0