Hydrogenation of Alkenes Catalyzed by Mn(I) Alkyl Complexes Bearing NHC Phosphine Ligands DOI Creative Commons
Daniel Zobernig, Berthold Stöger, Luı́s F. Veiros

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(22)

Published: Aug. 10, 2024

Abstract An efficient additive free hydrogenation of alkenes with molecular hydrogen is described. The pre‐catalyst a well‐defined bench stable Mn(I) alkyl complex bearing NHC phosphine ligand. These reactions are environmentally benign and atom economic, implementing an inexpensive, earth abundant non‐precious metal catalyst. catalytic process initiated by migratory insertion CO ligand into the Mn‐alkyl bond to yield acyl intermediate which undergoes rapid hydrogenolysis form active 16e hydride catalyst [Mn(PC‐ i Pr)(CO) 2 (H)]. A range mono‐ disubstituted were efficiently converted alkanes in good excellent yields. requires reaction temperature 60 °C. In all cases, loading 1 mol % pressure 50 bar was applied. mechanism based on DFT calculations presented supported experimental studies.

Language: Английский

Chemoselective Hydrogenation of α,β-Unsaturated Ketones Catalyzed by a Manganese(I) Hydride Complex DOI Creative Commons
Kartick Dey, Graham de Ruiter

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4173 - 4177

Published: May 13, 2024

Here, we report the chemoselective hydrogenation of α,β-unsaturated ketones catalyzed by a well-defined Mn(I) PCNHCP pincer complex [(PCNHCP)Mn(CO)2H] (1). The reaction is compatible with wide variety functional groups that include halides, esters, amides, nitriles, nitro, alkynes, and alkenes, for most substrates occurs readily at ambient hydrogen pressure (1–2 bar). Mechanistic studies deuterium labeling experiments reveal non-cooperative mechanism, which further discussed in this report.

Language: Английский

Citations

10
Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation DOI Creative Commons

Ekaterina S. Gulyaeva,

Ruqaya Buhaibeh, Mohamed Boundor

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(22)

Published: Feb. 7, 2024

Abstract Systematic modification of the chelating NHC‐phosphine ligand (NHC = N ‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac ‐[(Ph 2 PCH NHC)Mn(CO) 3 Br] has been performed and catalytic activity resulting complexes was evaluated using acetophenone as a benchmark substrate. While variation phosphine NHC moieties led to inferior results than for parent system, incorporation phenyl substituent into methylene bridge improved performance by ca . times providing maximal TON values range 15000–20000. Mechanistic investigation combining experimental computational studies allowed rationalize this beneficial effect an enhanced stabilization reaction intermediates including anionic hydride species PC(Ph)NHC)Mn(CO) H] − playing crucial role process. These highlight interest such carbon substitution strategy being rarely employed design chemically non‐innocent ligands.

Language: Английский

Citations

6
N-heterocyclic carbenes as bridgehead donors in metal pincer complexes DOI
Fengkai He, Konstantinos P. Zois, Demeter Tzeli

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 514, P. 215757 - 215757

Published: May 9, 2024

Language: Английский

Citations

5
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

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(4)

Published: Oct. 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

Language: Английский

Citations

10
Thioether–NHC bidentate manganese complexes as efficient phosphine-free catalysts for hydrogenation at room temperature DOI Creative Commons
Mariia Hruzd, Sabrina L. Kleynemeyer, Christophe Michon

et al.

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A series of four original phosphine-free thioether-NHC manganese complexes have been synthesised and fully characterized. These applied as efficient catalysts for the hydrogenation alkenes ketones at room temperature, with low catalyst loadings (TON up to 900).

Language: Английский

Citations

0
Cobalt‐Driven Cross‐Dehydrocoupling of Silanes and Amines for Silylamine Synthesis DOI
Ewelina Szafoni, Krzysztof Kuciński, Grzegorz Hreczycho

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(15)

Published: May 8, 2024

Abstract Cobalt complexes featuring triazine‐based PNP ligands have proven to be exceptionally active and chemoselective pre‐catalysts in facilitating the dehydrogenative coupling between silanes amines, leading synthesis of diverse aminosilanes. Notably, even challenging substrates exhibited high reactivity. The catalyst‘s unique feature avoiding with tertiary enhances process chemoselectivity. It facilitates a more precise silylamines possessing SiH 2 −N SiH−N motifs, overcoming challenges associated broader reactivity seen previous systems. In terms its remarkable chemoselectivity, it is also noteworthy that catalytic system exhibits both versatility efficacy converting untouched double triple carbon‐carbon bonds. This accomplishment particularly significant, given brought about by activity commonly employed catalysts competitive hydrosilylation process.

Language: Английский

Citations

2
Hydroboration of Terminal Alkynes Catalyzed by a Mn(I) Alkyl PCP Pincer Complex Following Two Diverging Pathways DOI Creative Commons
Daniel Zobernig, Berthold Stöger, Luı́s F. Veiros

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12385 - 12391

Published: Aug. 5, 2024

A stereo- and regioselective Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The reaction highly

Language: Английский

Citations

2
Nickel–PNN catalysed sustainable synthesis of polysubstituted quinolines under microwave irradiation DOI
Manali A. Mohite, Sonu Sheokand, Maravanji S. Balakrishna

et al.

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(20), P. 5959 - 5969

Published: Jan. 1, 2024

This manuscript describes the synthesis of triazolyl-pyridine-based pincer cationic and neutral nickel complexes their application in microwave-assisted quinolines.

Language: Английский

Citations

2
Hydroboration of Terminal Alkynes Catalyzed by a Mn(I) Alkyl PCP Pincer Complex following Two Diverging Pathways DOI Creative Commons
Karl Kirchner, Daniel Zobernig,

Berthold Stoeger

et al.

Published: June 26, 2024

A stereo- and regioselective Mn(I)-catalyzed hydroboration of terminal alkynes with pinacolborane (HBPin) is described. The reaction highly Z-selective in the case aryl E-selective aliphatic alkynes. requires no additives proceeds a catalyst loading 1 mol % at 50 - 70oC. most active pre-catalyst bench-stable alkyl Mn(I) complex cis-[Mn(PCP-iPr)(CO)2 (CH2CH2CH3)]. catalytic process initiated by migratory insertion CO ligand into Mn-alkyl bond to yield an acyl intermediate. This species undergoes C-H B-H cleavage alkyne (aromatic alkynes) HBPin (in forming acetylide boryl catalysts [Mn(PCP-iPr)(CO)(CCR)] [Mn(PCP-iPr)(CO)(BPin)], respectively. broad variety aromatic were efficiently selectively borylated. Mechanistic insights are provided based on experimental data DFT calculations. functionalized alkenes can be used for further applications cross-coupling reactions.

Language: Английский

Citations

1
Hydrogenation of Alkenes Catalyzed by Mn(I) Alkyl Complexes Bearing NHC Phosphine Ligands DOI Creative Commons
Daniel Zobernig, Berthold Stöger, Luı́s F. Veiros

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(22)

Published: Aug. 10, 2024

Abstract An efficient additive free hydrogenation of alkenes with molecular hydrogen is described. The pre‐catalyst a well‐defined bench stable Mn(I) alkyl complex bearing NHC phosphine ligand. These reactions are environmentally benign and atom economic, implementing an inexpensive, earth abundant non‐precious metal catalyst. catalytic process initiated by migratory insertion CO ligand into the Mn‐alkyl bond to yield acyl intermediate which undergoes rapid hydrogenolysis form active 16e hydride catalyst [Mn(PC‐ i Pr)(CO) 2 (H)]. A range mono‐ disubstituted were efficiently converted alkanes in good excellent yields. requires reaction temperature 60 °C. In all cases, loading 1 mol % pressure 50 bar was applied. mechanism based on DFT calculations presented supported experimental studies.

Language: Английский

Citations

0