Pincer-Ruthenium-Catalyzed Direct Formation of Fuel-Grade Alkanes via a Net-Decarboxylative Coupling of Alcohols DOI

Pran Gobinda Nandi,

Pabitra Maity,

Akshai Kumar

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 543 - 556

Published: Dec. 20, 2024

The net-decarboxylative coupling of low-molecular weight alcohols to high-molecular alkanes has been investigated using a series NNN pincer-Ru catalysts based on bis(imino)pyridine and 2,6-bis(benzimidazole-2-yl)pyridine ligands. Notably, majority the considered complexes, including Ru precursors, were either not very active or unselective giving alkene/alkane mixtures. However, in presence 0.5 equiv NaOH toluene at 140 °C, complex (MeBim2NNN)RuCl2(PPh3)2 ligand demonstrated high activity up 91% yield with 100% selectivity toward alkane (1,3-diphenyl propane) starting from 2-phenyl ethanol after 24 h reaction. On other hand, (iPr2NNN)RuCl2(PPh3) was found be least gave 14% 1,3-diphenyl propane 25% selectivity. Experimental mechanistic studies point evolution hydrogen (detected by GC) formic acid 1H NMR) during reaction along involvement organic intermediates such as α,β-unsaturated aldehydes. [(MeBim2NNN)RuCl(PPh3)2]Cl catalyzed transformation first-order dependence initial rate concentration both catalyst base. While poisoning experiments Hg revealed homogeneous well-defined molecular nature catalyst, few these species, resting state (MeBim2NNN)RuHCl (experimentally trapped its PPh3 adduct), have identified HRMS analysis NMR studies. DFT complement experimental findings indicate that more favorable hydrogenolysis path, dehydrogenolysis step is rate-determining (ΔG140‡ = 22.81 kcal/mol), it leads formation acetaldehyde (MeBim2NNN)RuHCl. corresponding cycle involved insertion propene into Ru–H bond RDS had relatively unfavorable barrier 27.81 kcal/mol. This work provides direct access jet-fuel-grade single-step, one-pot strategy offers great promise open exciting opportunities this important field study.

Language: Английский

Direct use of methanol instead of formaldehyde or paraformaldehyde: Acceptorless dehydrogenative coupling for the synthesis of arylhydrazones catalyzed by a metal–ligand iridium bifunctional catalyst DOI
Beixuan Dong,

Yiqian He,

Xiangchao Xu

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: 438, P. 115685 - 115685

Published: Aug. 3, 2024

Language: Английский

Citations

5
NNN-Ru complexes catalyzed β-methylation of alcohols using methanol via borrowing hydrogen approach DOI

Mengxuan Bai,

Ziying Zhong, Zhiqiang Hao

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116026 - 116026

Published: Feb. 1, 2025

Language: Английский

Citations

0
Efficient net transfer-dehydrogenation of glycerol: NNN pincer–Mn and manganese chloride as a catalyst unlocks the effortless production of lactic acid and isopropanol DOI

Akshara Bisarya,

Sunil Dhole,

Akshai Kumar

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(30), P. 12698 - 12709

Published: Jan. 1, 2024

Herein, a series of pincer-Mn complexes based on bis(imino)pyridine ligands the type

Language: Английский

Citations

3
Production of Lactic Acid via Catalytic Transfer Dehydrogenation of Glycerol Catalyzed by Base Metal Salt Ferrous Chloride and Its NNN Pincer-Iron Complexes DOI

Babu Venkateshappa,

Akshara Bisarya,

Pran Gobinda Nandi

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(33), P. 15294 - 15310

Published: Aug. 7, 2024

NNN-Bis(imino) pyridine-based pincer-Fe(II) complexes with an expected trigonal bipyramidal (TBP) geometry equilibrated to a rearranged ion pair of octahedral dicationic Fe complex containing two bis(imino)pyridine ligands that are neutralized by tetrahedral dianionic-[FeCl4]2–. Single-crystal X-ray diffraction (SCXRD), high-resolution mass spectrometry (HRMS), and UV–visible (UV–vis) studies suggested the equilibrium was dictated sterics R group on imine N, less-crowded groups tilting bulky ones favoring TBP geometry. Electron paramagnetic resonance (EPR) Evan's magnetic moment measurements indicated were Fe(II) in high-spin state. In solution, over period 7 days, these oxidized mixture low-spin Fe(III) species. These found be highly active toward transformation biodiesel waste glycerol value-added lactic acid (LA). Particularly, (Ph2NNN)FeCl2 (0.1 mol %) gave 91% LA 99% selectivity at 140 °C using 1.2 equiv NaOH. With 0.0001 % (Ph2NNN)FeCl2, very high turnovers (74% LA, 98% selectivity, 740 000 turnover number (TON) 4405 per hour (TOs/h)) obtained after days. EPR species catalyst, few which detected HRMS. Experiments Hg suggestive mostly homogeneous molecular nature catalyst minor contribution from heterogeneous nanoparticles.

Language: Английский

Citations

3
Reforming of ethanol to hydrogen and acetic acid catalyzed by pincer-ruthenium complexes DOI
Vinay Arora,

Sunil Dhole,

Akshai Kumar

et al.

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(23), P. 6699 - 6711

Published: Jan. 1, 2023

Herein, we report the exceptional activity of pincer-ruthenium catalysts in value-addition ethanol via its high yield conversion ( ca. 73%) to green hydrogen and precious acetic acid with selectivity 100%) under ambient conditions.

Language: Английский

Citations

8
β-Methylation of Primary Alcohols with Methanol Catalyzed by a Metal–Ligand Bifunctional Iridium Catalyst DOI

Yiqian He,

Lili Shi, Beixuan Dong

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(17), P. 12392 - 12400

Published: Aug. 1, 2024

The development of efficient methods for the direct introduction a methyl group into molecules is becoming increasingly important. Herein, β-methylation primary alcohols with methanol has been accomplished under environmentally benign conditions using [Cp*Ir(2,2′-bpyO)(H2O)] as catalyst. It was found that functional groups in ligand are crucially important activity iridium complex. Furthermore, mechanistic research and application potential our catalytic system also presented.

Language: Английский

Citations

2
Selective C- and N-Methylation of Secondary Alcohols and Nitroaromatics with Methanol Catalyzed by a New Ru(II)-Azo Complex DOI
Santana Chakraborty,

Subhankar Khanra,

Shuchismita Dutta

et al.

Organometallics, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 24, 2024

Language: Английский

Citations

0
Ruthenium catalyzed dehydrogenative α-C–H functionalization of β-naphthol using alcohols: a metal–ligand cooperative borrowing hydrogen approach DOI
Amit Kumar Guin, Santana Chakraborty,

Subhankar Khanra

et al.

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(12), P. 3540 - 3549

Published: Jan. 1, 2024

Chemoselective α-C–H functionalization of β-naphthol is achieved with inexpensive and readily available alcohols using a well-defined, air-stable, easy-to-prepare Ru( ii )-catalyst (1a) bearing redox-active tridentate pincer ( L 1a).

Language: Английский

Citations

0
Pincer-Ruthenium-Catalyzed Direct Formation of Fuel-Grade Alkanes via a Net-Decarboxylative Coupling of Alcohols DOI

Pran Gobinda Nandi,

Pabitra Maity,

Akshai Kumar

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 15(1), P. 543 - 556

Published: Dec. 20, 2024

The net-decarboxylative coupling of low-molecular weight alcohols to high-molecular alkanes has been investigated using a series NNN pincer-Ru catalysts based on bis(imino)pyridine and 2,6-bis(benzimidazole-2-yl)pyridine ligands. Notably, majority the considered complexes, including Ru precursors, were either not very active or unselective giving alkene/alkane mixtures. However, in presence 0.5 equiv NaOH toluene at 140 °C, complex (MeBim2NNN)RuCl2(PPh3)2 ligand demonstrated high activity up 91% yield with 100% selectivity toward alkane (1,3-diphenyl propane) starting from 2-phenyl ethanol after 24 h reaction. On other hand, (iPr2NNN)RuCl2(PPh3) was found be least gave 14% 1,3-diphenyl propane 25% selectivity. Experimental mechanistic studies point evolution hydrogen (detected by GC) formic acid 1H NMR) during reaction along involvement organic intermediates such as α,β-unsaturated aldehydes. [(MeBim2NNN)RuCl(PPh3)2]Cl catalyzed transformation first-order dependence initial rate concentration both catalyst base. While poisoning experiments Hg revealed homogeneous well-defined molecular nature catalyst, few these species, resting state (MeBim2NNN)RuHCl (experimentally trapped its PPh3 adduct), have identified HRMS analysis NMR studies. DFT complement experimental findings indicate that more favorable hydrogenolysis path, dehydrogenolysis step is rate-determining (ΔG140‡ = 22.81 kcal/mol), it leads formation acetaldehyde (MeBim2NNN)RuHCl. corresponding cycle involved insertion propene into Ru–H bond RDS had relatively unfavorable barrier 27.81 kcal/mol. This work provides direct access jet-fuel-grade single-step, one-pot strategy offers great promise open exciting opportunities this important field study.

Language: Английский

Citations

0