Recent advances in the selective semi-hydrogenation of alkyne to (E)-olefins

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(12), P. 1517 - 1533

Published: Jan. 1, 2024

This article highlights the recent advances on newer technologies and important methodologies directed to ( E )-olefins from alkynes.

Language: Английский

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Reaction sites optimization mediated by ligand coverage for semi‐hydrogenation of different alkynes

AIChE Journal, Journal Year: 2025, Volume and Issue: unknown

Published: April 9, 2025

Abstract Precise regulation of catalysts active sites is the key to optimizing activity. In this work, a strategy for modulating alkyne adsorption by modifying support proposed. A series Pd/ZSM‐5@PPh 3 ‐X with different coverage triphenylphosphine (PPh ) were synthesized. enable efficient semi‐hydrogenation alkynes under mild conditions. Specifically, catalyst lower surface ligand (Pd/ZSM‐5@PPh ‐2) exhibits preference hydrogenation 2‐methyl‐3‐butyn‐2‐ol, while higher ‐10) favors conversion phenylacetylene. Both maintain an alkene selectivity exceeding 94%. Comprehensive experimental, characterization, and computational analyses revealed that which adsorbs on palladium surface, PPh inhibits strong alkynes, thereby preventing self‐poisoning. Conversely, high redirects site phenylacetylene enhanced hydrogen spillover accelerates reaction. This ligand‐modulated offers guidance rational design chemoselective catalysts.

Language: Английский

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Renaissance in Alkyne Semihydrogenation: Mechanism, Selectivity, Functional Group Tolerance, and Applications in Organic Synthesis

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

Published: April 25, 2025

Alkenes constitute a significant class of chemical compounds with applications in the bulk, pharmaceutical, or perfume industry. Among known methods olefin production, semihydrogenation C-C triple bond seems to be most straightforward one. Nonetheless, success this reaction requires full control over diastereoselectivity, eradication parasitic process over-reduction migration double formed, and achieving satisfactory functional-group compatibility. The review demonstrates developments field alkyne period 2010-2022, selected papers published 2023 2024, emphasizing solutions above-mentioned limitations. We discuss mechanistic aspects transformation, including those related unconventional systems. includes examples organic synthesis, confirming considerable utility process. Finally, strategies enhance catalyst selectivity are summarized. For reader's convenience, we provided graphical guidebook catalytic systems, illustrating efficiency particular method.

Language: Английский

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Chloride, Alkoxide, or Silicon: The Bridging Ligand Dictates the Spin State in Dicobalt Expanded Pincer Complexes

Organometallics, Journal Year: 2024, Volume and Issue: 44(1), P. 94 - 104

Published: Nov. 28, 2024

We report the synthesis and characterization of a series high- low-spin dicobalt complexes tBuPNNP expanded pincer ligand. Reacting this dinucleating ligand in its neutral form with two equiv CoCl2(tetrahydrofuran)1.5 yields high-spin complex featuring one Co inside outside pocket. Performing same reaction presence equivalents KOtBu provides access to wherein both centers are bound within PNNP pocket, also features bridging OtBu either excess diethyl silane affords containing unusual Si-based ligands. These were investigated using NMR spectroscopy, XAS, single crystal X-ray structure determination, computational methods, showing that ligands best described as base-stabilized silylenes.

Language: Английский

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E‐selective Semi‐hydrogenation of Alkynes under Mild Conditions by a Diruthenium Hydride Complex

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(69)

Published: Aug. 18, 2022

The synthesis, characterization and catalytic activity of a new class diruthenium hydrido carbonyl complexes bound to the

Language: Английский

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Reversible Bimetallic Inhibition to Modulate Selectivity During Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Bimetallic complexes have demonstrated a great ability to enhance the activity of monometallic systems for bond activation and catalysis. In this work, we explore opposite approach: using second metal passivate another by reversible bimetallic inhibition. To do so synthesized family nine electrophilic gold formula Au(PR

Language: Английский

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Synthesis, spectroscopic characterization, crystal structure, DFT and Hirschfeld surface analysis of a manganese(I) complex ([Mn(P-NH-NH-P)(CO)2][BPh4])

Journal of Molecular Structure, Journal Year: 2023, Volume and Issue: 1291, P. 136028 - 136028

Published: June 15, 2023

Language: Английский

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Superior electrocatalytic hydrogen evolution activity of a triply bridged diruthenium(II) complex on carbon cloth support

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(47), P. 6011 - 6014

Published: Jan. 1, 2024

This article describes the structural authentication of a unique triply bridged [1](ClO

Language: Английский

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Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

A new unsymmetrical dinucleating PNNN ligand is reported, the versatility of which demonstrated by formation heterobimetallic, homobimetallic and monometallic complexes.

Language: Английский

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