Driving force effects in proton coupled electron transfer

Mauro C.M. Laranjeira; Rosemary A. Marusak; A. Graham Lappin

doi:10.1016/S0020-1693(99)00558-7

Driving force effects in proton coupled electron transfer

Mauro C.M. Laranjeira, Rosemary A. Marusak, A. Graham Lappin

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28 Scopus citations

Abstract

The rates of reduction of the nickel(III) oxime-imine complexes, [Ni(III)(Me₂L)]⁺ and [Ni(III)(Me₂LH)]²⁺ by the corresponding iron(II) species are determined. Comparisons with rates calculated with the use of Marcus theory reveal that reactions of [Fe(III)(Me₂LH)]⁺, where the electron transfer product is the highly acidic [Fe(III)(Me₂LH)]²⁺, show rate enhancements of several orders of magnitude. These are ascribed to a strong coupling of the electron transfer with the concomitant, thermodynamically favorable proton transfer. A free energy correlation supports this conclusion.

Original language	English (US)
Pages (from-to)	186-190
Number of pages	5
Journal	Inorganica Chimica Acta
Volume	300-302
DOIs	https://doi.org/10.1016/S0020-1693(99)00558-7
State	Published - Apr 30 2000
Externally published	Yes

Bibliographical note

Funding Information:
The authors thank CAPES (Brazil) for a maintenance grant to M.C.M.L.

Keywords

Electron transfer
Iron complexes
Nickel complexes
Oxime-imine complexes
Proton transfer

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title = "Driving force effects in proton coupled electron transfer",

abstract = "The rates of reduction of the nickel(III) oxime-imine complexes, [Ni(III)(Me2L)]+ and [Ni(III)(Me2LH)]2+ by the corresponding iron(II) species are determined. Comparisons with rates calculated with the use of Marcus theory reveal that reactions of [Fe(III)(Me2LH)]+, where the electron transfer product is the highly acidic [Fe(III)(Me2LH)]2+, show rate enhancements of several orders of magnitude. These are ascribed to a strong coupling of the electron transfer with the concomitant, thermodynamically favorable proton transfer. A free energy correlation supports this conclusion.",

keywords = "Electron transfer, Iron complexes, Nickel complexes, Oxime-imine complexes, Proton transfer",

author = "Laranjeira, {Mauro C.M.} and Marusak, {Rosemary A.} and Lappin, {A. Graham}",

note = "Funding Information: The authors thank CAPES (Brazil) for a maintenance grant to M.C.M.L.",

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doi = "10.1016/S0020-1693(99)00558-7",

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T1 - Driving force effects in proton coupled electron transfer

AU - Laranjeira, Mauro C.M.

AU - Marusak, Rosemary A.

AU - Lappin, A. Graham

N1 - Funding Information: The authors thank CAPES (Brazil) for a maintenance grant to M.C.M.L.

PY - 2000/4/30

Y1 - 2000/4/30

N2 - The rates of reduction of the nickel(III) oxime-imine complexes, [Ni(III)(Me2L)]+ and [Ni(III)(Me2LH)]2+ by the corresponding iron(II) species are determined. Comparisons with rates calculated with the use of Marcus theory reveal that reactions of [Fe(III)(Me2LH)]+, where the electron transfer product is the highly acidic [Fe(III)(Me2LH)]2+, show rate enhancements of several orders of magnitude. These are ascribed to a strong coupling of the electron transfer with the concomitant, thermodynamically favorable proton transfer. A free energy correlation supports this conclusion.

AB - The rates of reduction of the nickel(III) oxime-imine complexes, [Ni(III)(Me2L)]+ and [Ni(III)(Me2LH)]2+ by the corresponding iron(II) species are determined. Comparisons with rates calculated with the use of Marcus theory reveal that reactions of [Fe(III)(Me2LH)]+, where the electron transfer product is the highly acidic [Fe(III)(Me2LH)]2+, show rate enhancements of several orders of magnitude. These are ascribed to a strong coupling of the electron transfer with the concomitant, thermodynamically favorable proton transfer. A free energy correlation supports this conclusion.

KW - Electron transfer

KW - Iron complexes

KW - Nickel complexes

KW - Oxime-imine complexes

KW - Proton transfer

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DO - 10.1016/S0020-1693(99)00558-7

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SN - 0020-1693

VL - 300-302

SP - 186

EP - 190

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

ER -

Driving force effects in proton coupled electron transfer

Abstract

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Keywords

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