Electrocatalytic hydrogenation of unsaturated organic compounds with molecular complexes: Mechanistic views DOI Creative Commons
Gabriel Durin, Nicolas Kaeffer, Walter Leitner

и другие.

Current Opinion in Electrochemistry, Год журнала: 2023, Номер 41, С. 101371 - 101371

Опубликована: Авг. 10, 2023

Electrocatalytic hydrogenation of π-bonds in unsaturated organic compounds is a promising strategy for electrifying chemical synthesis using renewable energies. This approach not only offers an alternative to the use molecular hydrogen but also has potential unlock original reaction pathways with higher efficiencies or featuring distinct selectivities functional group tolerances. In this emerging field, such reactivity engineering can be ideally explored complexes based on fundamental understanding underlying mechanisms. Recent developments via electrocatalysis and related key mechanistic features are presented viewpoint. Perspectives drawn highlight less areas catalytic space point way improved systems.

Язык: Английский

Hydrogenation of Terminal Alkenes Catalyzed by Air‐Stable Mn(I) Complexes Bearing an N‐Heterocyclic Carbene‐Based PCP Pincer Ligand DOI Creative Commons
Daniel Zobernig,

Michael Luxner,

Berthold Stöger

и другие.

Chemistry - A European Journal, Год журнала: 2023, Номер 30(4)

Опубликована: Окт. 10, 2023

Efficient hydrogenations of terminal alkenes with molecular hydrogen catalyzed by well-defined bench stable Mn(I) complexes containing an N-heterocyclic carbene-based PCP pincer ligand are described. These reactions environmentally benign and atom economic, implementing inexpensive, earth abundant non-precious metal catalyst. A range aromatic aliphatic were efficiently converted into alkanes in good to excellent yields. The hydrogenation proceeds at 100 °C catalyst loadings 0.25-0.5 mol %, 2.5-5 % base (KO

Язык: Английский

Процитировано

10
Bimetallic MnxRu100–x Nanoparticles on Supported Ionic Liquid Phases (MnxRu100–x@SILP) as Tunable Hydrogenation Catalysts DOI Creative Commons
Johannes Zenner, Liqun Kang, Neha Antil

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3227 - 3235

Опубликована: Фев. 7, 2025

Процитировано

0
Manganese(I)-NNSe Pincer Complex Mediated Dehydrogenative Cyclization to Synthesize 2-Aryl-2,3-dihydroquinolin-4(1H)-ones DOI
Suman Mahala, Sohan Singh, P S Rakesh

и другие.

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

A catalytic one-pot cascade dehydrogenative cyclization of 1-(2-aminophenyl)ethanone using primary alcohols is presented. The reaction catalyzed by an earth-abundant manganese pincer complex NNSe ligand, without any solvent, additives, base, or hydrogen acceptor, liberating dihydrogen and water as the only byproducts. Compared to earlier reported four-step coupling protocol, a single step required synthesize 2-aryl-2,3-dihydroquinolin-4(1H)-ones.

Язык: Английский

Процитировано

0
Hydrosilylation of Ketones With Manganese(I) Thiopyridine Catalysts DOI Creative Commons

Antonia Reisenhofer,

Ferdinand Belaj, Malek Y. S. Ibrahim

и другие.

Applied Organometallic Chemistry, Год журнала: 2025, Номер 39(5)

Опубликована: Апрель 2, 2025

ABSTRACT Hydrosilylation of ketones using manganese complexes has emerged as an efficient and safer alternative to traditional reduction methods. Reported manganese(I) systems are typically monomeric Mn(I) carbonyl bromide catalysts, while dimeric have remained largely unexplored. Here, three the type [{Mn(6‐R‐PyS)(CO) 3 } 2 ] (R = H 1 , CH CF ) featuring thiopyridine ligands Mn S cores found be catalysts in visible light‐induced hydrosilylation at room temperature. Notably, optimal reactivity was achieved when irradiation wavelength set 427 nm. Furthermore, a catalyst loading 0.1 mol% sufficient achieve full conversion within 90 min over wide scope acetophenones aliphatic ketones. However, drastically reduced sterically demanding, electron withdrawing group introduced ligand. An induction time 10 observed that can attributed formation active species, after which reaction proceed without irradiation. Further investigations into mechanism revealed upon solutions complexes, CO is released forming undefined paramagnetic species. In conclusion, for fast catalysis with dinuclear unhindered activation light required. catalytic amenable continuous flow chemistry exemplified by acetophenone . When carried out photoflow reactor, completed 14.2‐min resistant time.

Язык: Английский

Процитировано

0
Manganese(I)‐Catalyzed Chemoselective Transfer Hydrogenation of the C=C Bond in Conjugated Ketones at Room Temperature DOI
Dipesh M. Sharma, Anand B. Shabade, Rajesh G. Gonnade

и другие.

Chemistry - A European Journal, Год журнала: 2023, Номер 29(43)

Опубликована: Май 16, 2023

Chemoselective transfer hydrogenation of C=C bond in α,β-unsaturated ketones is demonstrated at room temperature employing a manganese(I) catalyst and half an equivalent ammonia-borane (H3 N-BH3 ). A series mixed-donor pincer-ligated Mn(II) complexes, (tBu2 PN3 NPyz )MnX2 [κP ,κN -(N-(di-tert-butylphosphaneyl)-6-(1H-pyrazol-1-yl)pyridin-2-amine)MnX2 ] {X=Cl (Mn2), X=Br (Mn3), X=I (Mn4)} were synthesized characterized. Amongst the (Mn2, Mn3, Mn4) Mn(I) complex, )Mn(CO)2 Br (Mn1) screened; Mn1 acts as efficient for chemoselective reduction ketones. Various synthetically important functionalities like halides, methoxy, trifluoromethyl, benzyloxy, nitro, amine, unconjugated alkene alkyne groups, including heteroarenes, compatible provided saturated excellent yields (up to 97 %). preliminary mechanistic study highlighted crucial role metal-ligand (M-L) cooperation through dearomatization-aromatization process hydrogenation.

Язык: Английский

Процитировано

9
Hydrosilylation of Terminal Alkynes Catalyzed by an Air-Stable Manganese–NHC Complex DOI

Rakesh R. Behera,

Ratnakar Saha,

Alamsaty Ashis Kumar

и другие.

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 8133 - 8149

Опубликована: Июнь 15, 2023

In recent years, catalysis with base metal manganese has received a significant amount of interest. Catalysis complexes having N-heterocyclic carbenes (NHCs) is relatively underdeveloped in comparison to the extensively investigated catalysts possessing pincer ligands (particularly phosphine-based ligands). Herein, we describe synthesis two imidazolium salts decorated picolyl arms (L1 and L2) as NHC precursors. Facile coordination L1 L2 MnBr(CO)5 presence resulted formation manganese(I)-NHC (1 2) an air-stable solid good isolated yield. Single-crystal X-ray analysis revealed structure cationic [Mn(CO)3(NHC)][PF6] tridentate N,C,N binding ligand facile fashion. Along few known manganese(I) complexes, these Mn(I)-NHC 1 2 were tested for hydrosilylation terminal alkynes. Complex was proved be effective catalyst alkynes selectivity toward less thermodynamically stable β-(Z)-vinylsilanes. This method provided regioselectivity (anti-Markovnikov addition) stereoselectivity (β-(Z)-product). Experimental evidence suggested that present pathway involved organometallic mechanism manganese(I)-silyl species possible reactive intermediate.

Язык: Английский

Процитировано

9
Efficient Depolymerization of Polyester and Polycarbonate Plastic Waste Catalyzed by Commercially Available Homogeneous and Heterogeneous Manganese Catalysts DOI
Daniel L. Lourenço,

Daniela F. Oliveira,

Ana C. Fernandes

и другие.

Advanced Sustainable Systems, Год журнала: 2023, Номер 8(3)

Опубликована: Сен. 7, 2023

Abstract This work describes the depolymerization of several polyester and polycarbonate plastic waste in value‐added compounds catalyzed by air stable, cheap commercially available manganese Mn(OTf) 2 , Mn (CO) 10 MnBr(CO) 5 MeCpMn(CO) 3 using boranes silanes as reducing agents with good to excellent yields. Commercial heterogeneous catalyst, manganeses(II) ethyl/butyl phosphonate silica (Si‐Mn), has also proven be very efficient reductive a variety polyesters PC.BPA. The use Si‐Mn consecutive is investigated, showing that these catalysts remain their activity after reactions.

Язык: Английский

Процитировано

9
Tandem manganese catalysis for the chemo-, regio-, and stereoselective hydroboration of terminal alkynes: in situ precatalyst activation as a key to enhanced chemoselectivity DOI Creative Commons
Victor Duran Arroyo, Rebeca Arévalo

RSC Advances, Год журнала: 2024, Номер 14(8), С. 5514 - 5523

Опубликована: Янв. 1, 2024

The manganese( ii ) complex [Mn( iPr PNP)Cl 2 ] ( PNP = 2,6-bis(diisopropylphosphinomethyl)pyridine) was found to catalyze the stereo- and regioselective hydroboration of terminal alkynes employing HBPin (pinacolborane).

Язык: Английский

Процитировано

3
“Anion-Switchable” Pincer-Mn(I) Catalyst for the Reductive N-Methylation of Amines with Formic Acid and CO2 DOI Creative Commons
Sebastián Martínez‐Vivas, Sergio Gonell, Macarena Poyatos

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(10), С. 7600 - 7608

Опубликована: Май 1, 2024

We report a manganese(I) complex of formula [Mn(NDI-CNC)(CO)3](BArF4), in which NDI-CNC refers to pincer pyridine-bis-imidazolylidene ligand functionalized with naphthalene-diimide (NDI) moiety. Due the presence NDI fragment, electron-donating strength can be increased by producing an electrochemical reduction moiety or addition tetrabutylammonium chloride (TBACl). The extent changes produced power quantified studying variation C–O stretching frequencies infrared spectroscopy. It is observed that catalytic activity manganese reductive methylation series secondary amines formic acid (or CO2) PhSiH3 almost negligible, but catalyst turned very active TBACl. This study constitutes rare example anion-sensitive catalyst. Furthermore, switched on and off for several cycles subsequent TBACl NOBF4, respectively.

Язык: Английский

Процитировано

3
Selective oxidation of silanes into silanols with water using [MnBr(CO)5] as a precatalyst DOI Creative Commons
Emanuele Antico, Markus Leutzsch, Niklas Wessel

и другие.

Chemical Science, Год журнала: 2022, Номер 14(1), С. 54 - 60

Опубликована: Дек. 1, 2022

This study presents the use of MnBr(CO) 5 for selective conversion silanes to silanols with water as an oxidant generating valuable hydrogen only by-product.

Язык: Английский

Процитировано

12