Development and mechanistic investigation of the dehydrogenation of alcohols with an iron(iii) salen catalyst

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(23), P. 4794 - 4800

Published: Jan. 1, 2023

The iron(III) salen complex (R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamineiron(III) chloride has been developed as a catalyst for the acceptorless dehydrogenation of alcohols. catalyzes direct synthesis imines in good yields from different primary alcohols and amines with liberation hydrogen gas. mechanism investigated experimentally labelled substrates theoretically density functional theory calculations. In contrast to corresponding manganese(III) salen-catalyzed dehydrogenation, it not possible identify homogeneous catalytic pathway iron complex. Instead, poisoning experiments trimethylphosphine mercury indicated that catalytically active species are heterogeneous small particles.

Language: Английский

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NHC–amine Ru complex catalyzed selective mono-N-methylation of amines with methanol: understanding the effect of amine ligands

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 11(1), P. 113 - 119

Published: Nov. 14, 2023

The selective mono- N -methylation of amines with methanol by the bifunctional NHC–NH 2 Ru complex is presented.

Language: Английский

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Mechanistic insight into borrowing-hydrogenN-alkylation catalyzed by an MLC catalyst with dual proton-responsive sites

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(42), P. 16215 - 16223

Published: Jan. 1, 2022

Metal-ligand cooperation (MLC) catalysis is one of the most important concepts in field organometallic catalysis. However, diverse functional ligands result ambiguous mechanisms and constrain understanding MLC Herein, a theoretical study based on DFT calculations performed to shed light mechanistic preference borrowing-hydrogen N-alkylation catalysed by ruthenium complex with dual proton-responsive sites. The results suggest that reaction pathway mediated α-NH site requires overcoming higher activation energy barrier (31.4 kcal mol-1) compared γ-NH due ligand distortion after protonation. Nevertheless, instability caused does not transform into catalytic activity for subsequent hydrogenation reaction. In contrast, facilitates rate-determining hydride transfer step (21.1 via non-covalent interaction instead participating bond formation breaking process, which found be more plausible mechanism. These findings demonstrate versatile role N-H functionality, may provide useful guidance design new catalysts future.

Language: Английский

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Catalytic Fe2+ Cation Pair Site for Base‐free N‐Alkylation of Aromatic Amines with Alcohols

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

Published: Oct. 11, 2024

The development of heterogeneous Fe catalysts is very attractive due to the ubiquitous, abundant, and inexpensive nature as a resource. However, oxides are commonly inert hence, design fabrication active sites essential. Herein, an cation pair site by simple reduction treatment SiO

Language: Английский

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Remote C-H Bond Cooperation Strategy Enabled Silver Catalyzed Borrowing Hydrogen Reactions

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Metal–ligand cooperation (MLC) is an essential strategy in transition metal catalysis. Herein, we demonstrate a remote C–H bond that enables the unprecedented homogeneous Ag( i )-catalyzed BH/HA reaction.

Language: Английский

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