Electron‐Transfer Reactions of Electron‐Reservoir Complexes and Other Monoelectronic Redox Reagents in Transition‐Metal Chemistry

Astruc, Didier

doi:10.1002/9783527618248.ch27

Cited by 11 publications

(7 citation statements)

References 318 publications

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“…The oxidation potential of APy-H in dimethyl formamide (DMF) containing 0.1 M tetra- n -butylammonium hexafluorophosphate determined by means of cyclic voltammetry using ferrocene/ferrocinium as an internal reference (FeCp 2 0/+ = 0.47) is 0.60 ± 0.05 V vs SCE . Reduction potentials determined by square wave voltammetry for the pyrimidine deoxynucleosides T, C, U, Br U, and I U are −2.35, −2.48, −2.30, −1,86, and −1.82 ± 0.05 V vs SCE, respectively.…”

Section: Resultsmentioning

confidence: 99%

Dynamics of Photochemical Electron Injection and Efficiency of Electron Transport in DNA

et al. 2009

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Table S1. m/z values for oligomer sequences determined by MALDI-TOF mass spectrometry. Sequence Calculated Found Sequence Calculated Found APy-T 4886.3 4881.6 APy-1 Br U 4951.2 4948.2 APy-2 Br U 4951.2 4948.0 APy-2U 4872.3 4875.2 APy-3 Br U 4951.2 4948.3 APy-3U 4872.3 4869.5 APy-4 Br U 4951.2 4955.6 APy-4U 4872.3 4874.8 APy-5 Br U 5568.6 5576.7 APy-5U 5489.5 5489.1 APy-6 Br U 6186.0 6190.7 APy-6U 6107.1 6106.3 APy-7 Br U 6803.4 6805.4 APy-7U 6724.3 6726.9 APy-8 Br U 7420.9 7416.0 APy-8U 7341.8 7345.2 APy-2 I U 4998.3 4998.5 APy-2U 4872.3 4875.6 APy-3 I U 4998.3 4996.2 APy-3U 4872.3 4868.1 APy-4 I U 4998.3 4997.9 APy-4U 4872.3 4871.1 APy-5 I U 5615.7 5618.2 APy-5U 5489.6 5492.1

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Section: Resultsmentioning

confidence: 99%

Dynamics of Photochemical Electron Injection and Efficiency of Electron Transport in DNA

et al. 2009

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“…Anionic reagents are among the most effective electron donors (reductants) in both inorganic as well as organic redox systems; likewise, the best electron acceptors (oxidants) are commonly found to be cationic species. , As a result, it has long been recognized that the ion-pairing effects can play critical roles in mediating electron-transfer rates of charged donors and acceptors in solutions . However, such studies have been necessarily limited to qualitative descriptions of dynamic ion pairs owing to equilibration among various ionic structures that is readily subject to solvent effects. , …”

Section: Introductionmentioning

confidence: 99%

Intermolecular Electron-Transfer Mechanisms via Quantitative Structures and Ion-Pair Equilibria for Self-Exchange of Anionic (Dinitrobenzenide) Donors

Rosokha

Newton

et al. 2005

J. Am. Chem. Soc.

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Definitive X-ray structures of "separated" versus "contact" ion pairs, together with their spectral (UV-NIR, ESR) characterizations, provide the quantitative basis for evaluating the complex equilibria and intrinsic (self-exchange) electron-transfer rates for the potassium salts of p-dinitrobenzene radical anion (DNB(-)). Three principal types of ion pairs, K(L)(+)DNB(-), are designated as Classes S, M, and C via the specific ligation of K(+) with different macrocyclic polyether ligands (L). For Class S, the self-exchange rate constant for the separated ion pair (SIP) is essentially the same as that of the "free" anion, and we conclude that dinitrobenzenide reactivity is unaffected when the interionic distance in the separated ion pair is r(SIP) > or =6 Angstroms. For Class M, the dynamic equilibrium between the contact ion pair (with r(CIP) = 2.7 Angstroms) and its separated ion pair is quantitatively evaluated, and the rather minor fraction of SIP is nonetheless the principal contributor to the overall electron-transfer kinetics. For Class C, the SIP rate is limited by the slow rate of CIP right arrow over left arrow SIP interconversion, and the self-exchange proceeds via the contact ion pair by default. Theoretically, the electron-transfer rate constant for the separated ion pair is well-accommodated by the Marcus/Sutin two-state formulation when the precursor in Scheme 2 is identified as the "separated" inner-sphere complex (IS(SIP)) of cofacial DNB(-)/DNB dyads. By contrast, the significantly slower rate of self-exchange via the contact ion pair requires an associative mechanism (Scheme 3) in which the electron-transfer rate is strongly governed by cationic mobility of K(L)(+) within the "contact" precursor complex (IS(CIP)) according to the kinetics in Scheme 4.

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“…On the other hand, in order for the favorable generation of organocopper intermediates, alcohol solvents are suggested to use. Because copper(II) salts are widely used as single electron transfer oxidants in organic chemistry, ,,, observations made in this effort that solvents and additives control reactivities and redox properties of these oxidants could have far reaching importance. Finally, this study would also suggest that the interplay between solvents and redox reagents, particularly metal salts, is a crucial factor to govern ET reaction pathways in general …”

Section: Discussionmentioning

confidence: 90%

“…Although copper(II) salts are often employed as SET oxidants in organic chemistry, ,,, their use in inducing ring-opening reactions of cyclopropanol derivatives is limited. ,,, About three decades ago, Ryu and co-workers reported the results of seminal studies which demonstrated that Cu(BF 4 ) 2 promotes reactions of bicyclic cyclopropyl silyl ethers that form dimeric products (upper path in Scheme ). When these reactions are carried out in the presence of dimethyl acetylenedicarboxylate (DMAD) and water, addition of the β-acylalkyl species occurs to give Z -adducts.…”

Section: Introductionmentioning

confidence: 99%

Solvent-Dependent Reaction Pathways Operating in Copper(II) Tetrafluoroborate Promoted Oxidative Ring-Opening Reactions of Cyclopropyl Silyl Ethers

et al. 2016

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Oxidative ring-opening reactions of benzene-fused bicyclic cyclopropyl silyl ethers, promoted by copper(II) tetrafluoroborate, were investigated. The regioselectivity of cyclopropane ring-opening as well as product distributions were found to be highly dependent on the nature of the solvent. In alcohols, dimeric substances arising from external bond cleavage are major products. Radical rearrangement products are also formed in solvents such as ether and ethyl acetate. On the contrary, nucleophile addition to carbocation intermediates, generated by internal bond cleavage, occurs mainly in reactions taking place in acetonitrile. It is proposed that the observed solvent effects that govern the reaction pathways followed are a consequence of varying solvation of copper intermediates, which governs their reactivity and redox properties. In addition, the influence of counteranions of the copper salts, organonitriles, cyclic dienes, and substrate structures on the pathways followed in these reactions was also examined.

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Electron‐Transfer Reactions of Electron‐Reservoir Complexes and Other Monoelectronic Redox Reagents in Transition‐Metal Chemistry

Cited by 11 publications

References 318 publications

Dynamics of Photochemical Electron Injection and Efficiency of Electron Transport in DNA

Dynamics of Photochemical Electron Injection and Efficiency of Electron Transport in DNA

Intermolecular Electron-Transfer Mechanisms via Quantitative Structures and Ion-Pair Equilibria for Self-Exchange of Anionic (Dinitrobenzenide) Donors

Solvent-Dependent Reaction Pathways Operating in Copper(II) Tetrafluoroborate Promoted Oxidative Ring-Opening Reactions of Cyclopropyl Silyl Ethers

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