New Tricks for an Old Dog: Grubbs Catalysts Enable Efficient Hydrogen Production from Aqueous-Phase Methanol Reforming DOI
Qian Wang,

Jialing Lan,

Rong Z. Liang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2212 - 2222

Published: Jan. 31, 2022

Herein, we report a new application of the prize-winning Grubbs catalysts, which have been widely applied for olefin metathesis, hydrogen production from aqueous-phase methanol reforming under easily achievable conditions (1 atm, <100 °C) with negligible CO formation. Out catalysts tested, best turnover frequency (158 h–1) and number (11424, 72 h) were both achieved third-generation catalyst (G-III). The TOF was G-III is competitive when compared some results reported ( Chem. Rev. 2018, 118, 372−433). Also, found to be versatile dehydrogenation ethanol formic acid. Mechanistic studies DFT calculations shed light on reaction mechanism, involves an unusual substrate (solvent)-assisted six-membered-ring (σ-bond) metathesis pathway. This work should open up opportunities in design connection economy and, more generally, development clean renewable energies.

Language: Английский

Reversible catalysis DOI
Vincent Fourmond, Nicolas Plumeré, Christophe Léger

et al.

Nature Reviews Chemistry, Journal Year: 2021, Volume and Issue: 5(5), P. 348 - 360

Published: April 30, 2021

Language: Английский

Citations

55
Selective Room-Temperature Hydrogenation of Amides to Amines and Alcohols Catalyzed by a Ruthenium Pincer Complex and Mechanistic Insight DOI Creative Commons
Sayan Kar,

Michael Rauch,

Amit Kumar

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(10), P. 5511 - 5515

Published: April 21, 2020

We report a room-temperature protocol for the hydrogenation of various amides to produce amines and alcohols. Compared with most previous reports this transformation, which use high temperatures (typically, 100-200 °C) H2 pressures (10-100 bar), system proceeds under extremely mild conditions (RT, 5-10 bar H2). The is catalyzed by well-defined ruthenium-PNNH pincer complexes (0.5 mol %) potential dual modes metal-ligand cooperation. An unusual Ru-amidate complex was formed crystallographically characterized. Mechanistic investigations indicate that predominantly via Ru-N amido/amine

Language: Английский

Citations

52
Mild Amide Synthesis Using Nitrobenzene under Neutral Conditions DOI

Ni Xiong,

Yuanqi Dong,

Bin Xu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(26), P. 4766 - 4771

Published: June 27, 2022

Amide synthesis is one of the most important transformations in organic chemistry due to broad application pharmaceutical drugs and materials. In this report, we describe a mild protocol for amide formation using readily available nitroarenes as nitrogen sources an inexpensive iron complex catalyst. Because use pH-neutral conditions avoidance strong oxidant or reductant, wide range aromatic aliphatic aldehydes well with various functional groups could be tolerated well. A plausible mechanism proposed based on detailed studies, which catalyst initiates radical process solvent plays key role O-atom acceptor.

Language: Английский

Citations

36
Well-Defined Bis(NHC)Mn(I) Complex Catalyzed Tandem Transformation of α,β-Unsaturated Ketones to α-Methylated Ketones Using Methanol DOI

Kasturi Ganguli,

Adarsha Mandal, Sabuj Kundu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(19), P. 12444 - 12457

Published: Sept. 28, 2022

Tandem transformation of α,β-unsaturated ketones to α-methylated by utilizing methanol as both the hydrogen and C1 sources is reported in presence a phosphine-free bis-N-heterocyclic carbene-Mn(I) (bis-NHC-Mn(I)) catalyst. The dehydrogenative coupling between produces corresponding along with 1 equiv formaldehyde water. Among different bis-NHC-Mn(I) complexes, ethyl wingtip-substituted complex triflate counteranion showed highest catalytic activity. This system was highly effective for reductive methylation wide variety substrates including aromatic, heteroaromatic, aliphatic straight chains containing ketones. Notably, this methodology led synthesis pharmaceutically important drug molecules such eperisone lanperisone. Several control experiments, kinetic studies, Hammett density functional theory (DFT) calculations were carried out understand tandem process.

Language: Английский

Citations

36
New Tricks for an Old Dog: Grubbs Catalysts Enable Efficient Hydrogen Production from Aqueous-Phase Methanol Reforming DOI
Qian Wang,

Jialing Lan,

Rong Z. Liang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(4), P. 2212 - 2222

Published: Jan. 31, 2022

Herein, we report a new application of the prize-winning Grubbs catalysts, which have been widely applied for olefin metathesis, hydrogen production from aqueous-phase methanol reforming under easily achievable conditions (1 atm, <100 °C) with negligible CO formation. Out catalysts tested, best turnover frequency (158 h–1) and number (11424, 72 h) were both achieved third-generation catalyst (G-III). The TOF was G-III is competitive when compared some results reported ( Chem. Rev. 2018, 118, 372−433). Also, found to be versatile dehydrogenation ethanol formic acid. Mechanistic studies DFT calculations shed light on reaction mechanism, involves an unusual substrate (solvent)-assisted six-membered-ring (σ-bond) metathesis pathway. This work should open up opportunities in design connection economy and, more generally, development clean renewable energies.

Language: Английский

Citations

29