Homobimetallic Ruthenium(II) Complexes Catalysed Selective Transfer Hydrogenation of Aldehydes in Water DOI
Gopal Deshmukh, Thakur Rochak Kumar Rana, Gopalan Rajaraman

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract Herein we report chemoselective transfer hydrogenation (TH) of aldehydes in aqueous medium using a series homobimetallic Ru(II) catalysts. Two complexes ( Ru1 and Ru3 ) one monometallic complex Ru2 have been employed the catalytic reduction aldehydes. Bimetallic [( p ‐cymene) 2 (RuCl) L 3 ] is obtained from reaction Schiff base ligand 2,2′‐((1E,1′E)‐((3,3′,5,5′‐tetraisopropyl‐[1,1′‐biphenyl]‐4,4′diyl)bis(azaneylylidene))bis(methaneylylidene))bis(4‐bromophenol) H characterized by various spectroscopic analytical techniques. The use formic acid/formate buffer as hydride source catalyst loading 0.01 mol % or resulted conversion to corresponding alcohols good excellent yield. This method very efficient for selective presence other reducible functional groups. A 0.0001 sufficient achieve turnover frequency (TOF) 5.5×10 5 h −1 . Furthermore, can recycled reused six consecutives cycles without sacrificing efficiency. comparison results between bimetallic offers valuable insights into distinct reactivity patterns complexes, presumably originating cooperative effect. To understand detailed mechanism, explored mechanistic pathway DFT methods on reported catalysts models which indicate that addition aldehyde rate‐limiting cooperativity boost efficiency case dinuclear catalyst. pH dependent TH mechanism has investigated with aid NMR ESI‐MS

Language: Английский

A Dinuclear Ru(II) Schiff-Base Complex Catalyzed One-pot Synthesis of Quinolines through Acceptorless Dehydrogenative Coupling of Secondary Alcohols with 2-Nitrobenzyl Alcohol DOI Creative Commons
Gopal Deshmukh, Santosh J. Gharpure, Ramaswamy Murugavel

et al.

Published: Jan. 19, 2024

Dinuclear Ru(II) complexes [(p-cymene)2(RuCl)2L1]2X (X = BF4 (Ru1); X PF6 (Ru2)) and mononuclear [(p-cymene)(RuCl)L2]BF4 (Ru3) (where L1 N,N'-(3,3',5,5'-tetraisopropyl-[1,1'-biphenyl]-4,4'-diyl)bis(1-(pyridin-2-yl)methanimine); L2 N-(2,6-diisopropyl-phenyl)-1-(pyridin-2-yl)-methanimine) have been synthesized characterized by spectroscopic analytical techniques. Ru1 Ru2 orchestrate direct transformation 2-nitrobenzyl alcohols to quinolines under mild conditions with significant efficiency even when employed at a minimal catalyst loading of 0.1 mol%. Proportional experiments carried out the corresponding complex Ru3 keeping Ru content same (0.2 mol% Ru3) reveal superior activity bimetallic system for one-pot quinoline synthesis. Late-stage functionalization bioactive steroids scale-up synthesis, demonstrate practical applicability present system. A probable mechanism this conversion is proposed based on trapping many intermediates ESI-mass spectroscopy. These mechanistic studies further substantiated React-IR monitoring progress reaction in real-time.

Language: Английский

Citations

3
Interfacial synergy between atomically dispersed Co and encapsulated Co nanoparticles on carbon-based catalyst for efficient hydrogenation of nitroaromatics DOI

Qi Gan,

Jiajun Zhang, Yan Cao

et al.

Carbon, Journal Year: 2025, Volume and Issue: unknown, P. 120328 - 120328

Published: April 1, 2025

Language: Английский

Citations

0
Dinuclear Ru(II) Schiff Base Complex Catalyzed One-Pot Synthesis of Quinolines through Acceptorless Dehydrogenative Coupling of Secondary Alcohols with 2-Nitrobenzyl Alcohol DOI
Gopal Deshmukh, Santosh J. Gharpure, Ramaswamy Murugavel

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(10), P. 1190 - 1202

Published: May 10, 2024

Dinuclear Ru(II) complexes [(p-cymene)2(RuCl)2L1]2X (X = BF4 (Ru1); X PF6 (Ru2)) and mononuclear [(p-cymene)(RuCl)L2]BF4 (Ru3) (where L1 N,N′-(3,3′,5,5′-tetraisopropyl-[1,1′-biphenyl]-4,4′-diyl)bis(1-(pyridin-2-yl)methanimine); L2 N-(2,6-diisopropyl-phenyl)-1-(pyridin-2-yl)-methanimine) have been synthesized characterized by spectroscopic analytical techniques. Ru1 Ru2 orchestrate direct transformation of 2-nitrobenzyl alcohols to quinolines under mild conditions with significant efficiency even when employed at a minimal catalyst loading 0.1 mol %. Proportional experiments carried out the corresponding complex Ru3 keeping Ru content same (0.2 % Ru3) reveal superior activity bimetallic system for one-pot quinoline synthesis. Late-stage functionalization bioactive steroids scale-up synthesis demonstrate practical applicability present system. A probable mechanism this conversion is proposed based on trapping many intermediates ESI-mass spectroscopy. These mechanistic studies further substantiated ReactIR monitoring progress reaction in real time.

Language: Английский

Citations

3
Bimetallic Ru(II) Complex Catalysed β‐Alkylation of Secondary Alcohols and α‐Alkylation of Ketones: Selective Formation of Saturated Ketones DOI
Gopal Deshmukh, Ramaswamy Murugavel

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(24)

Published: March 29, 2024

Abstract Ru(II) bimetallic [( p ‐cymene) 2 (RuCl) L 1 ]2X (X=BF 4 ( Cat2 ); X=PF 6 Cat3 )) and monometallic ‐cymene)(RuCl)L ]BF Cat4 ) (where =N,N’‐(3,3’,5,5’‐tetraisopropyl‐[1,1’‐biphenyl]‐4,4’‐diyl)bis(1‐(pyridin‐2‐yl)methanimine); =N‐(2,6‐diisopropyl‐phenyl)‐1‐(pyridin‐2‐yl)‐methanimine) catalyse selective synthesis of saturated ketones using β‐alkylation secondary alcohol or α‐alkylation with primary alcohol. Notably, a single catalyst facilitates the oxidation both alcohols followed by condensation hydrogenation yielding α‐alkylated ketones. Remarkably, this system allows loading as low 0.01 mol% for 0.005 ketone, delivering access to wide array derivatives yields ~97 %. Complex , in particular, orchestrates one‐pot alkylation reactions high turnover frequency (TOF) 5.6 10 5 h −1 0.0001 mol%. A comparative study between complexes reveals that complex exhibits better selectivity formation presumably owing cooperative effect metal centres. The scale‐up highlights practical applicability catalytic approach. To delve into plausible mechanisms, we conducted initial investigations through meticulously controlled experiments spectroscopic analysis.

Language: Английский

Citations

2
Microwave-assisted Transfer Hydrogenation of Carbonyl and Nitro Compounds by Bimetallic Ru(II) cymene Complexes DOI
Ramaswamy Murugavel, Gopal Deshmukh

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

Published: March 25, 2024

Abstract We report an investigation of the microwave-assisted catalytic transfer hydrogenation (TH) carbonyl and nitro compounds by employing Ru(II) complexes: bimetallic [(p-cymene)2(RuCl)2L1]2X (X = BF4 (Cat2); X PF6 (Cat3)) mononuclear [(p-cymene)(RuCl)L2]BF4 (Cat4) (where L1 N,N′-(3,3′,5,5′-tetraisopropyl-[1,1′-biphenyl]-4,4′-diyl)bis(1-(pyridin-2-yl)methanimine) L2 N-(2,6-diisopropylphenyl)-1-(pyridin-2-yl)methanimine). At a low catalyst loading 0.01 mol% (Cat2/Cat3), broad range substrates, comprising aromatic as well aliphatic ketones aldehydes, undergo TH reaction in short time just 10 minutes. Additionally, chemoselective nitroaromatic is achieved under microwave irradiation presence Cat2 within 5 Control experiments demonstrate that heating conditions outperform conventional terms improved activity efficiency. The used at very 0.001 to achieve high TONs TOFs 7.7 × 104 2.3 105 h–1, respectively, for reaction. Spectrometry involving trapping intermediates are propose mechanism compounds.

Language: Английский

Citations

1
Dibenzothiophene Bridged Bis‐Bodipy and Bis‐Metal Dipyrrin Complexes DOI
Gurpreet Kaur, Mangalampalli Ravikanth

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(21)

Published: June 3, 2024

Abstract Dibenzothiophene (DBT) bridged bis ‐dipyrromethane was synthesized by treating readily available 4,6‐di( p ‐formylphenyl) dibenzothophene with pyrrole under acid catalyzed conditions. The DBT further oxidized DDQ to afford the ‐dipyrrin which used as a ligand prepare ‐BODIPY, ‐Ni(II) dipyrrin and ‐Pd(II) complexes BF 3 ⋅ Et 2 O, Ni(acac) Pd(acac) respectively mild reaction DBT‐bridged ‐BODIPY ‐metal were thoroughly characterized studied HR‐MS, 1D & 2D NMR, absorption, fluorescence, cyclic voltammetry DFT techniques. showed highly intense absorption band at ~500 nm along one low 340 whereas complex slightly broadened blue shifted high 490 additional 426 nm. fluorescent fluorescence 524 quantum yield of 0.031 ‐M(II) nonfluorescent. optimized structures revealed that BODIPY units are more planar dibenzophene moiety in an angle ∼5.68°. However, 3‐Pd 3‐Ni , M(II)‐dipyrrin much deviated from dibenzothiophene plane 12.81°–14.23°.

Language: Английский

Citations

0
Homobimetallic Ruthenium(II) Complexes Catalysed Selective Transfer Hydrogenation of Aldehydes in Water DOI
Gopal Deshmukh, Thakur Rochak Kumar Rana, Gopalan Rajaraman

et al.

Chemistry - An Asian Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 12, 2024

Abstract Herein we report chemoselective transfer hydrogenation (TH) of aldehydes in aqueous medium using a series homobimetallic Ru(II) catalysts. Two complexes ( Ru1 and Ru3 ) one monometallic complex Ru2 have been employed the catalytic reduction aldehydes. Bimetallic [( p ‐cymene) 2 (RuCl) L 3 ] is obtained from reaction Schiff base ligand 2,2′‐((1E,1′E)‐((3,3′,5,5′‐tetraisopropyl‐[1,1′‐biphenyl]‐4,4′diyl)bis(azaneylylidene))bis(methaneylylidene))bis(4‐bromophenol) H characterized by various spectroscopic analytical techniques. The use formic acid/formate buffer as hydride source catalyst loading 0.01 mol % or resulted conversion to corresponding alcohols good excellent yield. This method very efficient for selective presence other reducible functional groups. A 0.0001 sufficient achieve turnover frequency (TOF) 5.5×10 5 h −1 . Furthermore, can recycled reused six consecutives cycles without sacrificing efficiency. comparison results between bimetallic offers valuable insights into distinct reactivity patterns complexes, presumably originating cooperative effect. To understand detailed mechanism, explored mechanistic pathway DFT methods on reported catalysts models which indicate that addition aldehyde rate‐limiting cooperativity boost efficiency case dinuclear catalyst. pH dependent TH mechanism has investigated with aid NMR ESI‐MS

Language: Английский

Citations

0