Mechanisms of Electron Transfer Reactions: The Bridged Activated Complex

Haim, Albert

doi:10.1002/9780470166314.ch6

Cited by 78 publications

(7 citation statements)

References 171 publications

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“…This result suggests that the hypothesized U V -Fe III intermediate is short-lived and experiences a quick electron back transfer to return to the original Fe II and U VI species. Such a non-productive pathway is known as a dead-end intermediate pathway (Haim, 1983). To complete the reduction to U IV , a second electron needs to be transferred during the lifetime of the U V intermediate.…”

Section: Discussionmentioning

confidence: 99%

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

Boyanov

O’Loughlin

Roden

et al. 2007

Geochimica et Cosmochimica Acta

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Section: Discussionmentioning

confidence: 99%

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

Boyanov

O’Loughlin

Roden

et al. 2007

Geochimica et Cosmochimica Acta

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“…The nonbonded (outer-sphere) electron-transfer mechanism is typically a nonadiabatic multistep process. , In this case, the electron-transfer event is most probably the rate-determining step . On the other hand, the bonded (inner-sphere) electron-transfer mechanism is generally an adiabatic multistep process. Here, the electron-transfer step might not be rate-determining. , (Scheme ).…”

Section: Theoretical Background: Physicochemical Aspects Of Eda Compl...mentioning

confidence: 99%

Organic Synthesis Enabled by Light-Irradiation of EDA Complexes: Theoretical Background and Synthetic Applications

Lima¹,

Lima²,

et al. 2016

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In the past decades, the physicochemical properties of electron donor−acceptor, EDA, complexes (also called charge-transfer, CT, complexes) have been extensively studied, although their synthetic applications have been somewhat limited. However, in recent years, this scenario has started to change as an increasing number of examples have been reported. In this regard, this review aims to present and discuss the main aspects associated with the physicochemical properties of these complexes and a selection of synthetic photochemical applications in organic chemistry.

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“…These rate parameters are indicated in Table 2. The proposed structure for the ISC is Azide has been shown to be a good bridging ligand in some previously reported electron-transfer studies [29,30]. Davies and Espenson [31] reported that Co(CN) 5 N 3 3-reacts with V(II) via an inner-sphere mechanism in the presence of acid.…”

Section: Reaction In Aqueous Acidic Mediummentioning

confidence: 96%

Intermediate and ion-pair formation in the outer-sphere reactions between azido-pentacyanocobaltate(III) and iron(II) polypyridyl complexes in aqueous medium

Ogunlusi

Ige

Oyetunji

et al. 2009

Transition Met Chem

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The kinetics of the reactions between azidopentacyanocobaltate(III), Co(CN) 5 N 3 3-, and iron(II) polypyridyl complexes, Fe(LL) 3 2? (LL = bipy, phen), have been studied in both neutral and acidic aqueous solutions at I = 0.1 mol dm -3 NaCl. The reactions were carried out under pseudo-first-order conditions in which the concentration of Fe(LL) 3 2? was kept constant, and the second-order rate constants obtained for the reactions at 35°C were within the range of 0.156-0.219 dm 3 mol -1 s -1 for LL = bipy and 0.090-0.118 dm 3 mol -1 s -1 for LL = phen. Activation parameters were measured for these systems. The dependence of reaction rates on acid was studied in the range [H ? ] = 0.001-0.008 mol dm -3 . The reaction in acid medium shows interesting kinetics. Two reactive species were identified in acid medium, namely, the protonated cobalt complex and the azido-bridged binuclear complex. The electron-transfer process is proposed to go by mixed outerand inner-sphere mechanisms in acid medium, in which electron transfer through the bridged inner-sphere complex (k 5 ) is slower than through the outer-sphere path (k 4 ).

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Mechanisms of Electron Transfer Reactions: The Bridged Activated Complex

Cited by 78 publications

References 171 publications

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

Organic Synthesis Enabled by Light-Irradiation of EDA Complexes: Theoretical Background and Synthetic Applications

Intermediate and ion-pair formation in the outer-sphere reactions between azido-pentacyanocobaltate(III) and iron(II) polypyridyl complexes in aqueous medium

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