Thermodynamic Cards of Classic NADH Models and Their Related Photoexcited States Releasing Hydrides in Nine Elementary Steps and Their Applications

Molecules, Journal Year: 2025, Volume and Issue: 30(5), P. 1053 - 1053

Published: Feb. 25, 2025

Thermodynamic cards of three classic NADH models (XH), namely 1-benzyl-1,4-dihydronicotinamide (BNAH), Hantzsch ester (HEH), and 10-methyl-9,10-dihydroacridine (AcrH), as well their photoexcited states (XH*: BNAH*, HEH*, AcrH*) releasing hydrides in nine elementary steps acetonitrile are established. According to these thermodynamic cards, the reducing abilities XH* remarkably enhanced upon photoexcitation, rendering them thermodynamically highly potent electron, hydrogen atom, hydride donors. The application imine reduction is demonstrated detail, revealing that photoexcitation enables act better donors, transforming transfer process from unfeasible feasible. Most intriguingly, AcrH* identified most favorable hydride, atom donor among states. exceptional properties release inspire further investigation into excited wavelengths, potentials, state stabilities more organic hydrides, discovery novel effective reductants.

Language: Английский

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Thermodynamic H-Abstraction Abilities of Nitrogen Centered Radical Cations as Potential Hydrogen Atom Transfer Catalysts in Y–H Bond Functionalization

ACS Omega, Journal Year: 2024, Volume and Issue: 9(24), P. 26708 - 26718

Published: June 4, 2024

Y–H bond functionalization has always been the focus of research interest in area organic synthesis. Direct hydrogen atom transfer (HAT) from is one most efficient and practical methods to activate bond. Recently, nitrogen centered radical cations were broadly utilized as H-abstraction catalysts bonds via HAT process. As a type catalyst, H-affinity significant thermodynamic parameter quantitatively evaluate potentials cations. In this work, pKa values 120 protonated N-containing compounds acetonitrile (AN) are predicted, H-affinities AN derived reduction using Hess' law. This work focuses on abilities enrich molecule library novel or H-abstractors provides valuable guidelines for application functionalization.

Language: Английский

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Thermodynamic evaluations of the acceptorless dehydrogenation and hydrogenation of pre-aromatic and aromatic N-heterocycles in acetonitrile

RSC Advances, Journal Year: 2024, Volume and Issue: 14(1), P. 222 - 232

Published: Jan. 1, 2024

This work focuses on two new thermodynamic parameters of pre-aromatic and aromatic N-heterocycles to offer a precise insight into their chemical hydrogen storage hydrogenation reactions.

Language: Английский

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Establishing the Thermodynamic Cards of Dipine Models’ Oxidative Metabolism on 21 Potential Elementary Steps

Molecules, Journal Year: 2024, Volume and Issue: 29(15), P. 3706 - 3706

Published: Aug. 5, 2024

Dipines are a type of important antihypertensive drug as L-calcium channel blockers, whose core skeleton is the 1,4-dihydropyridine structure. Since dihydropyridine ring key structural factor for biological activity, thermodynamics aromatization significant feature parameter understanding mechanism and pathways dipine metabolism in vivo. Herein, 4-substituted-phenyl-2,6-dimethyl-3,5-diethyl-formate-1,4-dihydropyridines refined structurally closest models to investigate thermodynamic potential oxidative metabolism. In this work, cards models' on 21 elementary steps acetonitrile have been established. Based cards, properties related intermediates acting electrons, hydrides, hydrogen atoms, protons, two ions (atoms) donors discussed. Moreover, applied evaluate redox properties, judge or reveal possible models.

Language: Английский

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Thermodynamic Evaluations of Amines as Hydrides or Two Hydrogen Ions Reductants and Imines as Protons or Two Hydrogen Ions Acceptors, as Well as Their Application in Hydrogenation Reactions

ACS Omega, Journal Year: 2023, Volume and Issue: 8(35), P. 31984 - 31997

Published: Aug. 21, 2023

Since the hydrogenation of imines (X) and dehydrogenation amines (XH2) generally involve two hydrogen ions (H– + H+) transfer, thermodynamic abilities various releasing hydrides or as well accepting protons are important characteristic physical parameters. In this work, pKa values 84 protonated (XH+) in acetonitrile were predicted. Combining Gibbs free energy changes from our previous work with pKa(XH+) values, derived using Hess's law by constructing thermochemical cycles, evaluations reductants acceptors compared discussed. Eventually, practical application data for on feasibility, mechanism, possible elementary steps was shown discussed paper point thermodynamics.

Language: Английский

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Evaluation of Organic Hydride/Acid Pairs as a Type of Thermodynamic-Potential-Regulated Multisite Proton-Coupled Electron Transfer Reagents

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(9), P. 6205 - 6221

Published: April 18, 2024

Organic hydride/acid pairs have been reported as multisite proton-coupled electron transfer (MS-PCET) reagents in reductive MS-PCET reactions recently. Since the key step for an organic pair acting reagent is a chemical process of releasing formal hydrogen atom, bond dissociation free energy atom valuable thermodynamic parameter objectively evaluating potential to act reagent. Now, 216 hydrides demonstrated be type thermodynamically potential-regulated Without doubt, reflect change N-substituted from simple hydride reductants thermodynamically-regulated reagents, which could significantly expand availability novel reagents.

Language: Английский

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Ligand and metal-centred reactivity in 2,6-bis(imino)-1,4-dihydropyridinate Zn(ii) alkyls: the dual behaviour of an intriguing type of complex

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(29), P. 9940 - 9951

Published: Jan. 1, 2023

2,6-Bis(imino)-dihydropyridinate ligands in mononuclear organo and alkoxo-zinc compounds. When complexation chemistry mimics biological systems.

Language: Английский

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