Electron transfer. 34. A relationship between catalytic effectiveness and reduction potential

1978 ◽  
Vol 17 (7) ◽  
pp. 1827-1830 ◽  
Author(s):  
Y. T. Fanchiang ◽  
Edwin S. Gould
Keyword(s):  
Electron Transfer ◽  
Reduction Potential

scholarly journals Spectral Probe for Electron Transfer and Addition Reactions of Azide Radicals with Substituted Quinoxalin-2-Ones in Aqueous Solutions

2021 ◽  
Vol 22 (2) ◽  
pp. 633
Author(s):  
Konrad Skotnicki ◽  
Slawomir Ostrowski ◽  
Jan Cz. Dobrowolski ◽  
Julio R. De la Fuente ◽  
Alvaro Cañete ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Aqueous Solutions ◽  
Absorption Spectra ◽  
Density Functional ◽  
Reduction Potential ◽  
Biological Significance ◽  
Radical Cations ◽  
Basis Sets ◽  
Double Bonds ◽  
Reduction Potentials

The azide radical (N3●) is one of the most important one-electron oxidants used extensively in radiation chemistry studies involving molecules of biological significance. Generally, it was assumed that N3● reacts in aqueous solutions only by electron transfer. However, there were several reports indicating the possibility of N3● addition in aqueous solutions to organic compounds containing double bonds. The main purpose of this study was to find an experimental approach that allows a clear assignment of the nature of obtained products either to its one-electron oxidation or its addition products. Radiolysis of water provides a convenient source of one-electron oxidizing radicals characterized by a very broad range of reduction potentials. Two inorganic radicals (SO4●−, CO3●−) and Tl2+ ions with the reduction potentials higher, and one radical (SCN)2●− with the reduction potential slightly lower than the reduction potential of N3● were selected as dominant electron-acceptors. Transient absorption spectra formed in their reactions with a series of quinoxalin-2-one derivatives were confronted with absorption spectra formed from reactions of N3● with the same series of compounds. Cases, in which the absorption spectra formed in reactions involving N3● differ from the absorption spectra formed in the reactions involving other one-electron oxidants, strongly indicate that N3● is involved in the other reaction channel such as addition to double bonds. Moreover, it was shown that high-rate constants of reactions of N3● with quinoxalin-2-ones do not ultimately prove that they are electron transfer reactions. The optimized structures of the radical cations (7-R-3-MeQ)●+, radicals (7-R-3-MeQ)● and N3● adducts at the C2 carbon atom in pyrazine moiety and their absorption spectra are reasonably well reproduced by density functional theory quantum mechanics calculations employing the ωB97XD functional combined with the Dunning’s aug-cc-pVTZ correlation-consistent polarized basis sets augmented with diffuse functions.

Fluoreszenzlöschung alternierender und nicht-alternierender polycyclischer aromatischer Kohlenwasserstoffe durch Nitroverbindungen / Fluorescence Quenching of Alternant and Non-alternant Polycyclic Hydrocarbons by Nitro Compounds

1977 ◽  
Vol 32 (12) ◽  
pp. 1561-1563 ◽  
Author(s):  
M. Zander
Keyword(s):  
Electron Transfer ◽  
Fluorescence Quenching ◽  
Excitation Energy ◽  
Reduction Potential ◽  
Nitro Compounds ◽  
Polycyclic Hydrocarbons ◽  
Electron Transfer Mechanism ◽  
Diffusion Controlled ◽  
Polycyclic Aromatic ◽  
Alternant Hydrocarbons

Abstract Fluorescence Quenching of Alternant and Non-alternant Polycyclic Hydrocarbons by Nitro Compounds Fluorescence quenching of polycyclic aromatic hydro­ carbons by nitromethane or nitrobenzene in fluid solutions is due to an electron transfer mechanism. The non diffusion controlled rate constant of quenching is very much greater for alternant than for non-alternant hydrocarbons with equal singlet excitation energy. This is explained by the known more positive reduction potential of non-alternant compared to alternant hydrocarbons.

Kinetics and mechanism of oxidation of N,N′-dimethyl-9,9′-biacridanyl by some π acceptors and a one-electron oxidant

1985 ◽  
Vol 63 (2) ◽  
pp. 445-451 ◽  
Author(s):  
Allan K. Colter ◽  
Charles C. Lai ◽  
A. Gregg Parsons ◽  
N. Bruce Ramsey ◽  
Gunzi Saito
Keyword(s):  
Electron Transfer ◽  
Reduction Potential ◽  
Isotope Effects ◽  
Substituent Effects ◽  
Kinetic Isotope Effects ◽  
Spin Trapping ◽  
Single Electron Transfer ◽  
Kinetic Isotope ◽  
The One ◽  
Rule Out

Oxidation of N,N′-dimethyl-9,9′-biacridanyl (DD) has been investigated as a model for single electron transfer (SET)-initiated oxidation of NADH coenzyme models such as N-methylacridan (DH). Oxidants investigated cover a 1010-fold range of reactivity in acetonitrile and include the π acceptors 1,4-benzoquinone (BQ), 2,6-dichloro-1,4-benzoquinone (DCIBQ), p-chloranil (CA), 2,3-dicyanobenzoquinone (DCBQ), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 2,3-dicyano-5-nitro-1,4-naphthoquinone (DCNNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DCMTNF), 9-dicyanomethylene-2,4,5,7-tetranitrofluorene (DCMTENF), 7,7,8,8-tetracyanoquinodimethane (TCNQ), and tetracyanoethylene (TCNE), and the one-electron oxidant tris(2,2′-bipyridyl)cobalt(III), [Formula: see text] The oxidation product is, in every case, N-methylacridinium ion (D+). A mechanism involving a rate-determining electron transfer with simultaneous fragmentation to D+ and N-methyl-9-acridanyl radical (D•) is proposed. This mechanism is supported by the observed dependence of the rate on oxidant reduction potential, by spin-trapping experiments, by kinetic isotope effects in oxidation of 9,9′-dideuterio-DD, and by substituent effects in oxidation of 2,2′- and 3,3′-dimethoxy-DD. The rate of oxidation of DD relative to that of DH is 3.4 × 102 with [Formula: see text] and with the π acceptors varies from ea. 0.3 (BQ) to 8.1 × 104 (DCMTENF). The results rule out a SET-initiated mechanism for oxidation of DH by all of the oxidants studied except TCNQ and DCMTENF.

Optimizing electron transfer from CdSe QDs to hydrogenase for photocatalytic H2 production

2019 ◽  
Vol 55 (39) ◽  
pp. 5579-5582 ◽  
Author(s):  
Monica L. K. Sanchez ◽  
Chang-Hao Wu ◽  
Michael W. W. Adams ◽  
R. Brian Dyer
Keyword(s):  
Quantum Dots ◽  
Electron Transfer ◽  
Reduction Potential ◽  
H2 Production ◽  
Cdse Quantum Dots ◽  
Redox Mediators ◽  
Cdse Qds ◽  
Electron Shuttles ◽  
Hydrogenase Enzyme

A series of viologen related redox mediators of varying reduction potential has been characterized and their utility as electron shuttles between CdSe quantum dots and hydrogenase enzyme has been demonstrated.

Electronic structure of the oxidized and reduced blue copper sites: contributions to the electron transfer pathway, reduction potential, and geometry

1996 ◽  
Vol 243 (1-2) ◽  
pp. 67-78 ◽  
Author(s):  
Edward I. Solomon ◽  
Kevin W. Penfield ◽  
Andrew A. Gewirth ◽  
Michael D. Lowery ◽  
Susan E. Shadle ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electronic Structure ◽  
Reduction Potential ◽  
Blue Copper ◽  
Electron Transfer Pathway ◽  
Copper Sites

scholarly journals Synthesis, Spectroscopy and Electrochemistry in Relation to DFT Computed Energies of Ferrocene- and Ruthenocene-Containing -Diketonato Iridium(III) Heteroleptic Complexes. Structure of [(2-Pyridylphenyl)2Ir(RcCOCHCOCH3]

Molecules ◽  
2019 ◽  
Vol 24 (21) ◽  
pp. 3923 ◽  
Author(s):  
Buitendach ◽  
Conradie ◽  
Malan ◽  
Niemantsverdriet ◽  
Swarts
Keyword(s):  
Crystal Structure ◽  
Electron Transfer ◽  
Single Crystal ◽  
Molecular Orbital ◽  
Reduction Potential ◽  
Redox Couple ◽  
Heteroleptic Complexes ◽  
Highest Occupied Molecular Orbital ◽  
Accuracy Level ◽  
Voltammetric Studies

A series of new ferrocene- and ruthenocene-containing iridium(III) heteroleptic complexes of the type [(ppy)2Ir(RCOCHCOR′)], with ppy = 2-pyridylphenyl, R = Fc = FeII(η5-C5H4)(η5-C5H5) and R′ = CH3 (1) or Fc (2), as well as R = Rc = RuII(η5-C5H4)(η5-C5H5) and R′ = CH3 (3), Rc (4) or Fc (5) was synthesized via the reaction of appropriate metallocene-containing β-diketonato ligands with [(ppy)2(-Cl)Ir]2. The single crystal structure of 3 (monoclinic, P21/n, Z = 4) is described. Complexes 1–5 absorb light strongly in the region 280−480 nm the metallocenyl -diketonato substituents quench phosphorescence in 1–5. Cyclic and square wave voltammetric studies in CH2Cl2/[N(nBu)4][B(C6F5)4] allowed observation of a reversible IrIII/IV redox couple as well as well-resolved ferrocenyl (Fc) and ruthenocenyl (Rc) one-electron transfer steps in 1−5. The sequence of redox events is in the order Fc oxidation, then IrIII oxidation and finally ruthenocene oxidation, all in one-electron transfer steps. Generation of IrIV quenched phosphorescence in 6, [(ppy)2Ir(H3CCOCHCOCH3)]. This study made it possible to predict the IrIII/IV formal reduction potential from Gordy scale group electronegativities, χR and/or ΣχR′ of -diketonato pendent side groups as well as from DFT-calculated energies of the highest occupied molecular orbital of the species involved in the IrIII/IV oxidation at a 98 % accuracy level.

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